Diffusion-Hardened Medical Implant

ABSTRACT

The present invention relates to a new composition and medical implant made therefrom, the composition comprising a thick diffusion hardened zone, and preferably further comprising a ceramic layer. The present invention relates to orthopedic implants comprising the new composition, methods of making the new composition, and methods of making orthopedic implants comprising the new composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. provisional application Ser.No. 60/750,557, filed Dec. 15, 2005.

TECHNICAL FIELD

The present invention relates to a new composition of diffusion-hardenedoxidized zirconium. The new composition has application, for example, inarticulating and non-articulating surfaces of medical implants. Thepresent invention also relates to orthopedic implants comprising the newcomposition, methods of making the new composition, and methods ofmaking medical implants comprising the new composition. While thepresent implant composition is useful in hard-on-soft applications(e.g., a medical implant component of the present invention articulatingagainst polyethylene), the present invention also encompasses the use ofthis new medical implant composition in hard-on-hard applications (e.g.,the present composition articulating against itself or against otherhard materials and ceramics) in a hip, knee, spinal, or other implant.

BACKGROUND OF THE INVENTION

Medical implant materials, in particular orthopedic implant materials,must combine high strength, corrosion resistance and tissuecompatibility. The longevity of the implant is of prime importanceespecially if the recipient of the implant is relatively young becauseit is desirable that the implant function for the complete lifetime of apatient. Because certain metal alloys have the required mechanicalstrength and biocompatibility, they are ideal candidates for thefabrication of prostheses. These alloys include 316L stainless steel,chrome-cobalt-molybdenum alloys (Co—Cr), titanium alloys and morerecently zirconium alloys which have proven to be the most suitablematerials for the fabrication of load-bearing and non-load bearingprostheses.

To this end, oxidized zirconium orthopedic implants have been shown toreduce polyethylene wear significantly. The use of diffusion-hardenedoxide surfaces such as oxidized zirconium in orthopedic applications wasfirst demonstrated by Davidson in U.S. Pat. No. 5,037,438. Previousattempts have been made to produce oxidized zirconium coatings onzirconium parts for the purpose of increasing their abrasion resistance.One such process is disclosed in U.S. Pat. No. 3,615,885 to Watson whichdiscloses a procedure for developing thick (up to 0.23 mm) oxide layerson Zircaloy 2 and Zircaloy 4. However, this procedure results insignificant dimensional changes especially for parts having a thicknessbelow about 5 mm, and the oxide film produced does not exhibitespecially high abrasion resistance.

U.S. Pat. No. 2,987,352 to Watson discloses a method of producing ablue-black oxide coating on zirconium alloy parts for the purpose ofincreasing their abrasion resistance. Both U.S. Pat. No. 2,987,352 andU.S. Pat. No. 3,615,885 produce a zirconium oxide coating on zirconiumalloy by means of air oxidation. U.S. Pat. No. 3,615,885 continues theair oxidation long enough to produce a beige coating of greaterthickness than the blue-black coating of U.S. Pat. No. 2,987,352. Thisbeige coating does not have the wear resistance of the blue-blackcoating and is thus not applicable to many components where there aretwo work faces in close proximity. The beige coating wears down morequickly than the blue-black oxide coating with the resulting formationof oxidized zirconium particles and the loss of the integrity of theoxidized zirconium surface. With the loss of the oxide surface thezirconium metal is then exposed to its environment and can lead totransport of zirconium ions into the adjacent environment.

The blue-black coatings have a thickness which is less than that of thebeige coating although the hardness of the blue-black coating is higherthan that of the beige coating. This harder blue-black oxide coatinglends itself better to surfaces such as prosthetic devices. Although theblue-black coating is more abrasion resistant than the beige coating itis a relatively thin coating. It is therefore desirable to produce newand improved compositions that maintain the desirable properties of theblue-black coatings of the prior art (for example, increased abrasionresistance).

As discussed above, U.S. Pat. No. 5,037,438 to Davidson discloses amethod of producing zirconium alloy prostheses with a oxidized zirconiumsurface. U.S. Pat. No. 2,987,352 to Watson discloses a method ofproducing zirconium bearings with a oxidized zirconium surface. Theoxide coating produced is not always uniform in thickness and thenon-uniformity reduces the integrity of the bonding between thezirconium alloy and the oxide layer and the integrity of the bondingwithin the oxide layer. Both U.S. Pat. No. 2,987,352 and U.S. Pat. No.5,037,438 are incorporated by reference as though fully set forthherein.

In U.S. Pat. Nos. 6,447,550; 6,585,772 and pending U.S. application Ser.No. 10/942,464, Hunter, et al. describes methods for obtaining anoxidized zirconium coating of uniform thickness. Hunter teaches thatsuch is obtained by applying pre-oxidation treatment techniques and bymanipulation of substrate microstructure. The use of uniform thicknessoxide layer results in increased resistance to corrosion by the actionof the body fluids as well as other benefits and is biocompatible andstable over the lifetime of the recipient. U.S. Pat. Nos. 6,447,550;6,585,772 and pending U.S. application Ser. No. 10/942,464 areincorporated by reference as though fully set forth herein.

The oxidized zirconium surfaces of Davidson and Hunter (henceforthreferred as Davidson-type oxidized zirconium composition), while havingrelatively thick ceramic oxide or nitride layers, did not exhibit thickdiffusion hardened zones below the ceramic oxide or nitride. Thediffusion hardened zones of Davidson-type oxidized zirconiumcompositions had thicknesses of at most 1.5-2 microns and typically lessdepending upon the conditions used to produce the composition. FIG. 1shows the nano-hardness profile of Davidson-type oxidized zirconiumcomposition (FIG. 1 is taken from M. Long, L. Reister and G. Hunter,Proc. 24^(th) Annual Meeting of the Society For Biomaterials, April22-26, 1998, San Diego, Calif., USA). The diffusion zone of theDavidson-type oxidized zirconium is between 1.5 to 2 microns. The oxideis approximately 5 microns, hence the totality of the hardened zone inthe Davidson oxide is approximately 7 microns. While the resultingcompositions of Davidson and Hunter exhibited high wear resistance incomparison to those compositions available in the prior art, there isstill room for improvement.

The significant reduction in wear of polyethylene against oxidizedsurfaces is attributed to the ceramic nature of the oxide. The oxidizedzirconium implant typically has a 5 to 6 micron thick ceramic surface(zirconium oxide) that is formed by a thermally driven diffusion processin air. Beneath the zirconium oxide is a hard, oxygen-rich diffusionlayer of approximately 1.5 to 2 microns. The totality of hardened zones(oxide plus diffusion hardened alloy) render the implant resistant tomicroscopic abrasion (for example, from third bodies such as bonecement, bone chips, metal debris, etc.) and slightly less resistant tomacroscopic impact (surgical instrumentation and fromdislocation/subluxation contact with metallic acetabular shells). Thesmaller hardening depth of these implants renders them less than optimalfor hard-on-hard applications. In a hard-on-hard application such as ina hip joint, the material articulates against itself or another hardenedor non-hardened metal instead of polyethylene. The wear rates in suchtypes of implants could be as high as 1 micron per year. With thetotality of the hardened zone (oxide and diffusion zone) having athickness of less than 7 microns, Davidson-type oxidized zirconiumimplants, although representing the state-of-the-art when originallyintroduced and still quite useful, have room for improvement in suchapplications. Hunter et al (U.S. Pat. No. 6,726,725) teaches suchhard-on-hard applications for Davidson-type oxidized zirconiumcomponents. Hunter '725 teaches that the oxide thickness can beincreased up to 20 microns for such applications. But as will be shownherein, Davidson-type oxide compositions having such thicknesses,although highly wear-resistant, can have significant number of oxidelayer defects. Such defects can lead to localized spalling of the oxide.Also, in the Davidson-type composition below the oxide, there is arelatively small diffusion hardened zone. Thus, while the Davidson-typecompositions exhibited superior wear resistance compared to manyconventional materials, there is always room for improvement.

Currently, there are two primary types of hard-on-hard hip implants thatare available commercially, namely metal-on-metal andceramic-on-ceramic. The current standard material of metal-on-metalimplants is high carbon Co—Cr alloy. The major concern with themetal-on-metal implant is the metal ion release from the joint and itsunknown effects on the physiology of the human body. The advantage ofmetal-on-metal implants is that they can be used in larger sizes. Thelarger size of the implant allows greater range of motion. Themetal-on-metal implants have also been shown to be useful forresurfacing type of application where conservation of bone is desired.In such larger joints, the conventional or cross-linked polyethylene isnot preferred and metal-on-metal may be the only choice available. Thelarger size requires polyethylene liner to be thinner. A thinner linermay not be mechanically strong, may creep more or may lead to increasedwear and osteolysis and eventually failure of the implant.

The other commonly used hard-on-hard implant material isceramic-on-ceramic. The current standard material of ceramic-on-ceramicimplants is alumina. Metal ion release is typically not a concern forthese implants. But due to limited toughness and the brittle nature ofceramics, it is difficult to make these implants in larger sizes. Theceramic components have finite probability of fracture thus leading to apotential joint failure and complications associated with the fractureof a joint.

It has been an object of much of the prior art to reduce the metal ionrelease and minimize the fracture risk by combining metal and ceramiccomponents. Fisher et al (U.S. Patent Application 2005/0033442) andKhandkar et al. (U.S. Pat. No. 6,881,229) teach using a metal-on-ceramicarticulation. Fisher et al teach that the difference in hardness betweenthe metallic component and the ceramic component to be at least 4000MPa. Khandkar et. al. specifically teach use of silicon nitride ceramiccomponents for articulating against the metallic component. In bothinstances the objective is to lower the wear of mating couples. But inboth instances, the fracture risk of ceramic is still significant. Theobject of the present invention is to eliminate the risk of fracturealong with metal ion release. It is eliminated by using a metalliccomponent with ceramic surface and diffusion hardened zone below theceramic surface. As mentioned in the details of the invention, diffusionhardened composition of present invention provides a solution to theabove described problems pertaining to hard-on-hard bearings made fromDavidson-type oxidized zirconium, high carbon CoCr (cobalt-chromium) andalumina. In one aspect of invention, the invented composition isapplicable in knee joints and in spinal joints where hard-on-hardarticulation is desired.

Unlike the Davidson-type oxidized zirconium, the oxidized zirconiumcomposition disclosed herein is significantly less susceptible to damagecaused by dislocation and subluxation. Thus, while the application ofdiffusion-hardened oxide layers such as Davidson-type oxidized zirconiumto orthopedic implants represented a great improvement in the art ofimplant materials, resulting in substantial improvements in abrasionresistance and service life, the new compositions of the presentinvention represent improvements over the Davidson-type compositions.

Production of a diffusion hardened zone in zirconium (and its alloys)and titanium (and its alloys) has been disclosed previously. One of theapproach suggested by Kemp (U.S. Pat. No. 5,399,207) is to oxidize azirconium alloy in a temperature range of 426° C. (800° F.) to 871° C.(1600° F.) for two hours or more. The approach of Kemp is to run theprocess longer so that oxygen diffuses farther into the substrate whilethe oxidation is taking place. The major disadvantage of this approachis higher temperature and prolonged time is required to form a thickerdiffusion zone. The higher temperature and prolonged time can lead tomicrostructural changes in the substrate and to a defective oxide thatcomprises substantial amounts of cracks and pores. Kemp teaches theapplication of its method on a Zircadyne 702 substrate. Following theteachings of Kemp, Zircadyne 702 and medical grade Zr-2.5Nb (ASTM F2384)were oxidized at 800° C. The oxide thickness of Zircadyne-702 sampleswas 10 to 12 micron whereas that of Zr-2.5Nb was approximately 20microns (FIGS. 2( a) and 2(b)). The diffusion hardened zone on bothsamples was approximately 25 microns (FIG. 2( c)). The oxide of bothsamples showed substantial defects in the form of cracks and pores.

In another approach, Davidson (U.S. Pat. No. 5,372,660) teachesoxidizing Ti alloy that contains Zr. The presence of Zr in Ti leads toformation of an oxide and a thicker diffusion zone. Following theteachings of Davidson an alloy of Ti—Zr—Nb (55% Ti w/w, 35% Zr w/w and10% Nb w/w) and medical grade Zr-2.5 Nb were oxidized in air. The alloysamples were oxidized at 635° C. for 6 hours. FIG. 3 showsmetallographic images showing the oxide and diffusion hardened zone. Theoxide of both Ti—Zr—Nb and Zr—2.5Nb is cracked. The oxide of Ti—Zr—Nbappears to separate from the substrate at several locations. FIG. 3 (c)shows micro-hardness of diffusion hardened zone. The Ti—Zr—Nb alloyshows approximately 10 to 15 micron thick diffusion hardened zone. Thediffusion hardened zone of Zr-2.5Nb is less than 5 microns. Thusfollowing the teachings of Kemp and Davidson, a significant depth ofhardening could be obtained but at the cost of substantial defects inthe resulting oxide. Kemp teaches a prolonged treatment at elevatedtemperatures, whereas Davidson teaches changing the chemistry of thealloy to form a thicker diffusion hardened zone. But in both cases theoxide formed is full of defects. Such type of defects in the oxide cancompromise integrity of the oxide and may lead to localized spalling.One of the compositions disclosed herein comprises a thick diffusionzone along with a substantially defect-free oxide. The oxide disclosedherein has additional distinctions over the prior art that will bedisclosed further in the details herein. The Davidson-type and Kemp-typeoxidized zirconium product is an oxide that is predominantly singlephase. The oxide of the present invention comprises a secondary phasethat is ceramic or oxygen-rich metal. Embodiments of the diffusionhardened zone of the present invention have a layered structure and apreferred hardness profile.

Another approach to produce a diffusion hardened metallic zone isbasically one of forming an oxide on the surface of the article bytreatment in an oxygen-rich environment, followed by heat treating thearticle in an oxygen-deficient environment. One of the approachesprovided by Takamura (Trans JIM, vol. 3, 1962, p. 10) has been tooxidize a titanium sample followed by treating it in argon gas (i.e., anoxygen deficient environment with a low partial pressure of oxygen).This apparently allows oxygen to diffuse in the substrate and form athick diffusion zone. Presence of oxygen in the diffusion zone leads tohardening. Another approach suggested by Dong et al (U.S. Pat. No.6,833,197) is to use vacuum or an inert gas mixture to achieve anoxygen-deficient environment, thereby achieving the diffusion-hardeningafter oxidation. The preferred temperature specified by both Takamuraand Dong et al for oxidation is 850° C. and that for diffusion hardening(vacuum treatment) is 850° C. Dong et al suggest this methodology fortitanium and zirconium and titanium/zirconium alloys. One of theproblems with these methods, particularly for zirconium alloys, is thatthe oxidation and diffusion hardening temperatures are significantlyhigh and can lead to thick and cracked (defective) oxide as well ascracks in the substrates after diffusion hardening. Dong demonstratesits method using titanium alloys; no examples forzirconium/niobium-based or titanium/zirconium/niobium-based alloys havebeen shown.

Both Takamura and Dong et. al. recommend a preferred temperature ofoxidation and inert gas/vacuum treatment of 850° C. Following theirteachings, samples of Ti-6Al-4V and medical grade Zr-2.5Nb were oxidizedat 850° C. for 0.3 hr in air. FIGS. 4( a) and 4(b) show metallographicimages after oxidation. The oxide on the Ti-6Al-4V is less than 1 micronthick. The oxide does not seem to adhere well to the substrate. Theoxide on Zr-2.5Nb is approximately 12 microns thick and it is cracked.Following the teachings of Dong, both samples were subjected to vacuumtreatment under pressure of 10-4 torr and at 850° C. for 22 hours. FIGS.4( c) and 4(d) show metallographic images after vacuum treatment. Inboth samples, oxide has dissolved into the substrate. There are novisible cracks in Ti-6Al-4V sample. The crack is still present on thesurface of the Zr-2.5Nb sample. The crack appears to have propagatedinside the substrate during the vacuum treatment. These types of crackson the surface can significantly reduce fatigue strength of the alloy.The new composition and method of the present invention overcomes thesedeficiencies.

In order to further demonstrate the difference in the behavior betweenTi and Zr alloys, samples of Ti-6Al-4V and Zr-2.5Nb were oxidized at alower temperature (600° C. for 75 minutes). These samples were thentreated under vacuum (<10⁻⁴ torr) at 685° C. for 10 hours. As will bedisclosed further herein, the treatment was carried out in such a waythat oxide is partially retained on the Zr-2.5Nb substrate. FIGS. 5( a)and 5(b) show metallographic images of the oxide formed on Ti-6Al-4V andZr-2.5Nb samples. The oxide on Ti-6Al-4V is less than 0.1 micron whereasit is approximately 3 micron on Zr sample. No cracks are visible on bothsamples. After vacuum diffusion hardening, oxide on a Ti-6Al-4V sampleis completely dissolved whereas approximately 1 micron oxide is retainedon a Zr-2.5Nb sample (FIGS. 5( c) and 5(d)). FIG. 5( e) shows thehardness profile of the diffusion zone. Oxygen diffused almost entirelythrough the Ti alloy sample and thus produced a negligibly small depthof hardening whereas it did produce a significant depth of hardening inZr alloy. This example further illustrates the differences in Zr and Tialloys in the Dong process. It is evident from these examples that therange of temperatures that may work for Zr alloys may not be optimal forTi alloys and vice versa. Dong also teaches a sigmoid shaped hardnessprofile of the diffusion hardened metallic zone. The sigmoid shapeddiffusion hardened zone profile requires almost complete dissolution ofthe oxide in the substrate. The inventors of the present invention havefound that this is not necessary. The inventors have found that in oneaspect of this invention, it is advantageous to retain the oxide on thesurface during this process. This is accomplished by careful selectionof temperature and time for oxidation and subsequent diffusionhardening. Dong does not teach or suggest retention of the oxide on thesurface of the sample at the end of the vacuum treatment and obtainingdifferent types of oxygen concentration or hardness profiles other thana sigmoid profile when the oxide is almost completely dissolved.

In another approach of the prior art, Treco (R. Treco, J. Electrochem.Soc., Vol. 109, p. 208, 1962) used vacuum annealing method to completelydissolve the oxide formed on Zircalloy-2 after corrosion testing. Theobjective of Treco's work was to eliminate the oxide by vacuum annealingand the resultant diffusion zone by acid pickling. Treco neitherdiscloses advantage of retaining the oxide during diffusion process nordiscloses an application where such surfaces could be used. Finally,both Dong and Treco do not disclose use of such a technique to form aceramic oxide and diffusion hardened zone to make a damage resistantmedical implant.

The inventors have found that the damage (i.e., wear) resistance ofdiffusion hardened medical implant compositions can be improved byincreasing the thickness of totality of the hardened zones. Theresulting diffusion hardened medical implant compositions are new andnot disclosed or suggested in the prior art. The desired totality ofhardened zones can be achieved by varying the thicknesses of the ceramicoxide (or nitride, or mixed oxide/nitride) and the underlying diffusionhardened zone(s). Additionally, an increase in the thickness of thediffusion hardened zone imparts additional wear resistance desired inhard-on-hard articulation. A thicker diffusion hardened zone exhibits alayered structure in which the concentration of the diffusion hardeningspecies varies with depth. Careful consideration needs to be applied inselecting the temperature and time of oxidation and diffusion hardeningto achieve the desired totality of the hardened zones, while retaining(or enhancing) most of the mechanical, and electrochemical properties ofthe articles. Furthermore, the proper conditions for the processes ofmanufacture of such compositions are related to the alloy system underconsideration. Such hardened alloys are suitable for articulationagainst soft polymers (such as ultra high molecular weight polyethylene(UHMWPE), cross-linked polyethylene (XLPE), polyurethane, etc and inhard-on-hard bearing applications against like hardened alloys, againstCoCr alloys, ceramics (alumina, silicon nitride, silicon carbide,zirconia, etc), other hard materials such as diamond, diamond-likecarbon and ceramic coatings (metal-oxides, metal-nitrides,metal-carbides and diamond), etc.

All of the above-referenced U.S. patents and published U.S. patentapplications are incorporated by reference as though fully describedherein.

BRIEF SUMMARY OF THE INVENTION

In one aspect of the present invention there is a medical implantcomprising: a substrate comprising zirconium or zirconium alloy; adiffusion hardened zone in contact with said substrate, said diffusionhardened zone comprising zirconium or zirconium alloy and a diffusionhardening species, said diffusion hardened zone having a thickness ofgreater than 2 microns; and, a substantially defect-free ceramic layerin contact with said diffusion hardened zone and comprising a surface ofsaid medical implant, said ceramic layer ranging in thickness from 0.1to 25 microns; and, wherein the total thickness of the ceramic layer andthe diffusion hardened zone is 5 microns or greater. In someembodiments, the ceramic layer comprises a secondary phase, and thediffusion hardened zone has a layered structure comprising at least twodistinct layers under metallographic analysis, the layered structurecharacterized by: a first layer directly below the ceramic layer,wherein the first layer is predominantly alpha phase zirconium; aninterface between the first layer and the ceramic layer; and; a secondlayer directly below the first layer. In some embodiments, the substratefurther comprises titanium, tantalum, hafnium, niobium, and anycombination thereof. In some embodiments, the diffusion hardeningspecies is selected from the group consisting of oxygen, nitrogen,boron, carbon, and any combination thereof. Preferably, the diffusionhardening species comprises oxygen. In some embodiments, the diffusionhardened zone has a concentration of oxygen which decreases in thedirection of the substrate, said decrease of oxygen concentration beingdefined by a function selected from the group consisting of an errorfunction, an exponential function, a near uniform distribution function,and any sequential combination thereof. In some embodiments, the ceramicoxide has monoclinic content of greater than 93%. In some embodiments,the diffusion hardened zone has a hardness profile which is defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function, and anysequential combination thereof. In some embodiments, thed first layerhas a thickness which is greater than or equal to the thickness of saidsecond layer and of any subsequent layers if present. In someembodiments, the diffusion hardened zone has a thickness of 5 to 70microns. The diffusion hardened zone may have a thickness of 10 to 50microns. The diffusion hardened zone may have a thickness of 15 to 30microns. In some embodiments, the hardness of the diffusion hardenedzone is at least 10% greater than that of the substrate In someembodiments, the medical implant is selected from the group consistingof a hip implant, a knee implant, and a spinal implant. In someembodiments, the substrate comprises an alloy of zirconium and niobiumand has a niobium content of at least 1% (w/w). The substrate maycomprise an alloy of zirconium and niobium has a niobium content of atleast 10% (w/w). In some embodiments, the medical implant furthercomprises an oxygen-containing zirconium alloy overlaying said ceramicoxide or nitride on the surface of said implant, said alloy being in themetallic state.

In another aspect of the present invention there is a medical implantcomprising: a substrate comprising zirconium or zirconium alloy; adiffusion hardened zone in contact with said substrate, said diffusionhardened zone comprising zirconium or zirconium alloy and a diffusionhardening species, said diffusion hardened zone having a thickness ofgreater than 5 microns; and, wherein the diffusion hardened zone has alayered structure comprising at least two distinct layers undermetallographic analysis, said layered structure characterized by: afirst layer on a surface of the implant; a second layer directly belowsaid first layer, wherein said first layer is predominantly alpha phasezirconium; and, said layered structure having a concentration ofdiffusion hardening species which decreases in the direction of thesubstrate, said decrease of concentration of diffusion hardening speciesbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof. In some embodiments,the substrate further comprises titanium, tantalum, hafnium, niobium,and any combination thereof. In some embodiments, the diffusionhardening species is selected from the group consisting of oxygen,nitrogen, boron, carbon, and any combination thereof. Preferably, thediffusion hardening species comprises oxygen. In some embodiments, thediffusion hardened zone has a concentration of oxygen which decreases inthe direction of the substrate, said decrease of oxygen concentrationbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof. In some embodiments,the diffusion hardened zone has a hardness profile which is defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function anysequential combination thereof. In some embodiments, the first layer hasa thickness which is greater than the thickness of said second layer andof any subsequent layers if present. In some embodiments, the diffusionhardened zone has a thickness of 5 to 70 microns. The diffusion hardenedzone may have a thickness of 10 to 50 microns. The diffusion hardenedzone may have a thickness of 15 to 30 microns. In some embodiments, thehardness of the diffusion hardened zone is at least 10% greater thanthat of the substrate. In some embodiments, the medical implant isselected from the group consisting of a hip implant, a knee implant, anda spinal implant. In some embodiments, the substrate comprises an alloyof zirconium and niobium has a niobium content of at least 1% (w/w). Thesubstrate may comprise an alloy of zirconium, titanium and niobium andhas a niobium content of at least 10% (w/w).

In another aspect of the present invention there is a method of making asurface hardened medical implant comprising the steps of: forming saidmedical implant of zirconium or zirconium alloy; and, further treatingsaid implant by any one of (a), (b), or (c), wherein (a), (b), and (c)are defined as follows: (a) treating said implant in the presence ofceramic-forming species at a temperature of less than 700° C. forgreater than 5 minutes; and, thereafter treating said implant undervacuum or inert gas at a temperature of from 500° C. to 1000° C. forgreater than 1 hour; (b) treating said implant in the presence ofceramic-forming species at a temperature of from 500° C. to 1000° C.;and, thereafter treating said implant under vacuum or inert gas at atemperature less than 700° C.; (c) treating said implant in the presenceof ceramic-forming species at a temperature of less than 700° C.; and,thereafter treating said implant under vacuum or inert gas at atemperature less than 700° C. In some embodiments, the method furthercomprises the step of treating said implant in the presence of aceramic-forming species at a temperature less than 700° C. for greaterthan 5 minutes after said step of thereafter treating said implant undervacuum or inert gas. In some embodiments, the step of thereaftertreating said implant under vacuum or inert gas is performed at atemperature of 600° C. to 700° C. In some embodiments, the step oftreating said implant in the presence of ceramic-forming species isperformed for between 5 minutes to 12 hours. In some embodiments, thestep of thereafter treating said implant under vacuum or inert gas isperformed for between 15 minutes to 30 hours. In some embodiments, thestep of forming a medical implant of zirconium or zirconium alloycomprises forming said medical implant of zirconium alloy having analloying element selected from the group consisting of titanium,tantalum, hafnium, niobium, and any combination thereof. In someembodiments, the step of forming comprises forming said medical implantof an alloy of zirconium and niobium, said alloy having a niobiumcontent of at least 1% (w/w). In some embodiments, the step of formingcomprises forming said medical implant of an alloy of zirconium andniobium, said alloy having a niobium content of at least 10% (w/w). Insome embodiments, the step of treating said implant in the presence ofceramic-forming species and said step of thereafter treating saidimplant under vacuum or inert gas comprise treating said implant with adiffusion hardening species selected from the group consisting ofoxygen, nitrogen, boron, carbon, and any combination thereof.

In another aspect of the present invention there is a method of makingsurface hardened medical implant comprising steps of: forming saidmedical implant of zirconium or zirconium alloy; forming an oxide,carbide, nitride, boride or combination thereof, on a surface of saidimplant at a temperature of from 500° C. to 1000° C. for greater than 2hours; removing the formed oxide, carbide, nitride, boride, orcombination thereof; and, thereafter re-forming an oxide, carbide,nitride, boride, or combination thereof, on a surface of said implant ata temperature of from 500° C. to 1000° C. for greater than 5 minutes.

In another aspect of the present invention there is a method of makingsurface hardened medical implant comprising steps of: forming saidmedical implant of zirconium or zirconium alloy; diffusing oxygen ornitrogen into said implant at a partial pressure of oxygen or nitrogenof less than 0.05 bar and at a temperature ranging from 500° C. to 1000°C. for greater than 2 hours; and, thereafter oxidizing or nitriding theimplant between 500° C. to 1000° C. for greater than 10 minutes.

In another aspect of the present invention there is a method of making asurface hardened medical implant comprising the steps of: forming saidmedical implant of zirconium or zirconium alloy; oxidizing or nitridingsaid implant at a temperature of from 500° C. to 700° C. to form atleast a 2 micron thick oxide or nitride; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C. toretain at least 0.1 microns oxide, to form at least 0.005 micronsmetallic hardened layer, and to form a diffusion zone having a thicknessof at least 2 microns. In some embodiments, the substrate furthercomprises titanium, tantalum, niobium, hafnium, and any combinationthereof. In some embodiments, the oxide or nitride thickness before saidstep of thereafter treating said implant under vacuum or inert gas isfrom 2 to 15 microns. In some embodiments, the oxide or nitridethickness after said step of thereafter treating said implant undervacuum or inert gas is from 0.1 to 10 microns. In some embodiments, thediffusion hardened zone is from 2 to 50 microns.

In another aspect of the present invention there is a medical implantproduced by the process comprising the steps of: forming said medicalimplant of zirconium or zirconium alloy; further treating said implantby any one of (a), (b), or (c), wherein (a), (b), and (c) are defined asfollows: (a) treating said implant in the presence of ceramic-formingspecies at a temperature of less than 700° C. for greater than 5minutes; and, thereafter treating said implant under vacuum or inert gasat a temperature of from 500° C. to 1000° C. for greater than 1 hour;(b) treating said implant in the presence of ceramic-forming species ata temperature of from 500° C. to 1000° C.; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C.;(c) treating said implant in the presence of ceramic-forming species ata temperature of less than 700° C.; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C.

In another aspect of the present invention there is a medical implant,comprising: (a) a first implant portion comprising zirconium orzirconium alloy, said first implant portion having a bearing surface;(b) a second implant portion comprising zirconium or zirconium alloy,said second implant portion having bearing surface; (c) wherein thebearing surface of said first implant portion and the bearing surface ofsaid second implant portion each have a size and shape to engage orcooperate with one another; (d) a diffusion hardened zone in contactwith at least a portion of said zirconium or zirconium alloy, saiddiffusion hardened zone forming at least a part of the bearing surfaceof both of said first and second implant portions, said diffusionhardened zone comprising zirconium or zirconium alloy and a diffusionhardening species, said diffusion hardened zone having a thickness ofgreater than 2 microns; and, (e) a substantially defect-free ceramiclayer in contact with said diffusion hardened zone and comprising asurface of said medical implant, said ceramic layer ranging in thicknessfrom 0.1 to 25 microns; wherein the total thickness of the ceramic layerand the diffusion hardened zone is 5 microns or greater. In someembodiments, the ceramic layer comprises a secondary phase; and, thediffusion hardened zone has a layered structure comprising at least twodistinct layers under metallographic analysis, the layered structurecharacterized by: a first layer directly below the ceramic layer,wherein the first layer is predominantly alpha phase zirconium; aninterface between the first layer and the ceramic layer; and; a secondlayer directly below the first layer. In some embodiments, the substratefurther comprises titanium, tantalum, hafnium, niobium, and anycombination thereof. In some embodiments, the diffusion hardeningspecies is selected from the group consisting of oxygen, nitrogen,boron, carbon, and any combination thereof. Preferably, the diffusionhardening species comprises oxygen. In some embodiments, the diffusionhardened zone has a concentration of oxygen which decreases in thedirection of the substrate, said decrease of oxygen concentration beingdefined by a function selected from the group consisting of an errorfunction, an exponential function, a near uniform distribution function,and any sequential combination thereof. In some embodiments, the ceramicoxide has monoclinic content of greater than 93%. In some embodiments,the diffusion hardened zone has a hardness profile which is defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function and anysequential combination thereof. In some embodiments, the first layer hasa thickness which is greater than or equal to the thickness of saidsecond layer and of any subsequent layers if present. In someembodiments, the diffusion hardened zone has a thickness of 5 to 70microns. Tthe diffusion hardened zone may have a thickness of 10 to 50microns. The diffusion hardened zone may have a thickness of 15 to 30microns. In some embodiments, the hardness of the diffusion hardenedzone is at least 10% greater than that of the substrate. In someembodiments, the medical implant is selected from the group consistingof a hip implant, a knee implant, and a spinal implant. In someembodiments, the substrate comprises an alloy of zirconium and niobiumand has a niobium content of at least 1% (w/w). In some embodiments, thesubstrate comprises an alloy of zirconium and niobium has a niobiumcontent of at least 10% (w/w). In some embodiments, the medical implantfurther comprises an oxygen-containing zirconium alloy overlaying saidceramic oxide or nitride on the surface of said implant, said alloybeing in the metallic state.

In another aspect of the present invention, there is medical implant,comprising: (a) a first implant portion comprising zirconium orzirconium alloy, said first implant portion having a bearing surface;(b) a second implant portion comprising zirconium or zirconium alloy,said second implant portion having bearing surface; (c) wherein thebearing surface of said first implant portion and the bearing surface ofsaid second implant portion each have a size and shape to engage orcooperate with one another; (d) a diffusion hardened zone in contactwith at least a portion of said zirconium or zirconium alloy, saiddiffusion hardened zone forming at least a part of the bearing surfaceof both of said first and second implant portions, said diffusionhardened zone comprising zirconium or zirconium alloy and a diffusionhardening species, said diffusion hardened zone having a thickness ofgreater than 5 microns; wherein the diffusion hardened zone has alayered structure comprising at least two distinct layers undermetallographic analysis, said layered structure characterized by: afirst layer on a surface of the implant; a second layer directly belowsaid first layer, wherein said first layer is predominantly alpha phasezirconium; and, said diffusion hardened zone having a concentration ofdiffusion hardening species which decreases in the direction of thesubstrate, said decrease of concentration of diffusion hardening speciesbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof. In some embodiments,the substrate further comprises titanium, tantalum, hafnium, niobium,and any combination thereof. In some embodiments, the diffusionhardening species is selected from the group consisting of oxygen,nitrogen, boron, carbon, and any combination thereof. Preferably, thediffusion hardening species comprises oxygen. In some embodiments, thediffusion hardened zone has a concentration of oxygen which decreases inthe direction of the substrate, said decrease of oxygen concentrationbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof. In some embodiments,the diffusion hardened zone has a hardness profile which is defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function and anysequential combination thereof. In some embodiments, the first layer hasa thickness which is greater than the thickness of said second layer andof any subsequent layers if present. In some embodiments, the diffusionhardened zone has a thickness of 5 to 70 microns. The diffusion hardenedzone may have a thickness of 10 to 50 microns. The diffusion hardenedzone may have a thickness of 15 to 30 microns In some embodiments, thehardness of the diffusion hardened zone is at least 10% greater thanthat of the substrate. In some embodiments, the medical implant isselected from the group consisting of a hip implant, a knee implant, anda spinal implant. In some embodiments, the substrate comprises an alloyof zirconium and niobium has a niobium content of at least 1% (w/w). Insome embodiments, the substrate comprises an alloy of zirconium,titanium and niobium and has a niobium content of at least 10% (w/w).

In another aspect of the present invention, there is a medical implantcomprising: (a) a first implant portion, said first implant portionhaving a bearing surface; (b) a second implant portion, said secondimplant portion having a bearing surface; (c) wherein the bearingsurface of said first implant portion and the bearing surface of saidsecond implant portion each have a size and shape to engage or cooperatewith one another; (d) wherein one or both of the two portions of themedical implant comprises a biocompatible alloy having an elasticmodulus less than 200 GPa; and, (e) wherein the difference in radius ofthe mating portions is greater than about 50 microns. In someembodiments, one or both of said first implant portion and said secondimplant portion further comprises: a substrate; a diffusion hardenedzone in contact with said substrate, said diffusion hardened zonecomprising a diffusion hardening species, said diffusion hardened zonehaving a thickness of greater than 2 microns; and, a substantiallydefect-free ceramic layer in contact with said diffusion hardened zoneand comprising a surface of said medical implant, said ceramic layerranging in thickness from 0.1 to 25 microns; and, wherein the totalthickness of the ceramic layer and the diffusion hardened zone is 5microns or greater. In some embodiments, one or both of said firstimplant portion and said second implant portion further comprises: theceramic layer comprises a secondary phase; and, the diffusion hardenedzone has a layered structure comprising at least two distinct layersunder metallographic analysis, the layered structure characterized by: afirst layer directly below the ceramic layer; an interface between thefirst layer and the ceramic layer; and; a second layer directly belowthe first layer. In some embodiments, one or both of said first implantportion and said second implant portion further comprises: a substrate;a diffusion hardened zone in contact with said substrate, said diffusionhardened zone comprising a diffusion hardening species, said diffusionhardened zone having a thickness of greater than 5 microns; and, whereinthe diffusion hardened zone has a layered structure comprising at leasttwo distinct layers under metallographic analysis, said layeredstructure characterized by: a first layer on a surface of the implant; asecond layer directly below said first layer; and, said diffusionhardened zone having a concentration of diffusion hardening specieswhich decreases in the direction of the substrate, said decrease ofconcentration of diffusion hardening species being defined by a functionselected from the group consisting of an error function, an exponentialfunction, a near uniform distribution function, and any sequentialcombination thereof. In some embodiments, one or both of said firstimplant portion and said second implant portion further comprises: asubstrate; a diffusion hardened zone in contact with said substrate,said diffusion hardened zone comprising a diffusion hardening species,said diffusion hardened zone having a thickness of greater than 2microns; and, a substantially defect-free ceramic layer in contact withsaid diffusion hardened zone and comprising a surface of said medicalimplant, said ceramic layer ranging in thickness from 0.1 to 25 microns;and, wherein the total thickness of the ceramic layer and the diffusionhardened zone is 5 microns or greater. In some embodiments, one or bothof said first implant portion and said second implant portion furthercomprises: the ceramic layer comprises a secondary phase; and, thediffusion hardened zone has a layered structure comprising at least twodistinct layers under metallographic analysis, the layered structurecharacterized by: a first layer directly below the ceramic layer; aninterface between the first layer and the ceramic layer; and; a secondlayer directly below the first layer.

The foregoing has outlined rather broadly the features and technicaladvantages of the present invention in order that the detaileddescription of the invention that follows may be better understood.Additional features and advantages of the invention will be describedhereinafter which form the subject of the claims of the invention. Itshould be appreciated by those skilled in the art that the conceptionand specific embodiment disclosed may be readily utilized as a basis formodifying or designing other structures for carrying out the samepurposes of the present invention. It should also be realized by thoseskilled in the art that such equivalent constructions do not depart fromthe spirit and scope of the invention as set forth in the appendedclaims. The novel features which are believed to be characteristic ofthe invention, both as to its organization and method of operation,together with further objects and advantages will be better understoodfrom the following description when considered in connection with theaccompanying figures. It is to be expressly understood, however, thateach of the figures is provided for the purpose of illustration anddescription only and is not intended as a definition of the limits ofthe present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, reference isnow made to the following descriptions taken in conjunction with theaccompanying drawing, in which:

FIG. 1 shows the hardness profile of Davidson-type oxidized zirconiumcomposition. The thickness of the diffusion zone is 1.5 to 2 microns(Long et. al.)

FIGS. 2( a) and (b) are metallographic images of Zircadyne 702 andZr-2.5Nb oxidized following the teachings of Kemp; (c) micro-hardnessprofile of the diffusion hardened zone

FIGS. 3( a) and (b) are metallographic images of Ti—Zr—Nb and Zr-2.5Nboxidized by following teachings of Davidson; (c) Micro-hardness profileof diffusion hardened zone.

FIGS. 4( a) and (b) show samples of Ti-6Al-4V and Zr-2.5Nb oxidized at850° C. for 0.3 hours respectively; (c) and (d) show samples ofTi-6Al-4V and Zr-2.5Nb diffusion hardened at 850° C. for 22 hoursrespectively.

FIGS. 5( a) and (b) show samples of Ti-6Al-4V and Zr-2.5Nb oxidized at600° C. for 75 minutes respectively; (c) and (d) show samples ofTi-6Al-4V and Zr-2.5Nb diffusion hardened at 685° C. for 10 hoursrespectively, (e) shows the hardness profile of Ti-6Al-4V and Zr-2.5Nbafter diffusion hardening.

FIG. 6 shows hardness profiles obtained on Zr-2.5Nb samples after vacuumdiffusion process (685° C. for 10 hours). The starting oxide representsoxide thickness prior to vacuum diffusion treatment. The oxidation wascarried out at 635° C. for different times to produce different startingoxide thickness.

FIG. 7 shows metallographic images of samples with hardness profileobtained in FIG. 3 were re-oxidized at 635° C. for 60 minutes.

FIG. 8 illustrates Rockwell indents showing the damage resistance of (a)and (b) Davidson-type oxidized zirconium composition and (c) and (d)composition disclosed in this invention with a total hardening depth of20 to 25 microns.

FIG. 9 shows wear results of pin-on-disk testing of high carbon castCoCr against itself and one of the oxidized zirconium compositionsagainst itself (total hardened zone 20 to 25 microns) disclosed in thisinvention.

FIG. 10 shows the oxygen concentration profile of the diffusion zone.Analyses were carried out using a scanning auger microprobe withaccelerating voltage of 10 kV; probe current of 18 nA and electron beamat 30° from sample normal. Oxide was retained on the sample after thevacuum treatment.

FIG. 11 illustrates the micro-hardness profile of Davidson-type oxidizedzirconium composition and some of the compositions disclosed in thisinvention. Micro-hardness was carried out using a Knoop indenter at aload of 10 g.

FIG. 12 shows cross-sectional metallographic images; (a) Davidson-typeoxidized zirconium composition, (b) oxidized at 635° C. for 75 minutesand diffusion hardened at 585° C. for 10 hours, (c) oxidized at 690° C.for 60 minutes and diffusion hardened at 685° C. for 20 hours, and (d)oxidized at 635° C. for 75 minutes and diffusion hardened at 750° C. for20 hours. The dotted lines on the images show the demarcation of layers.

FIG. 13 shows XRD pattern of (a) Davidson-type oxidized zirconium and(b) one of the compositions of this invention. The M(−111) and M(111)are from −111 and 111 plane, T(111) is from tetragonal 111 plane. TheT(111) peak for new composition is negligible indicating smallertetragonal phase in the oxide compared to the oxide of Davidson-typeoxidized zirconium. The monoclinic phase analysis was carried using ASTMF 1873.

FIG. 14( a) and (b) show a Davidson-type oxidized zirconium composition;(c) and (d) show one of the compositions of this invention. The sampleshown in (c) and (d) was oxidized at 690° C. for 60 minutes anddiffusion hardened at 685° C. for 20 hours. The oxide was retained onthe surface. This is a longitudinal cross-section of the sample. Theorientation of secondary phase is different in transverse section. Adotted line is drawn to show how far the secondary phase is present inthe oxide. The samples are imaged using back scattered electron modewith accelerating voltage of 20 kV.

FIG. 15 illustrates (a) an oxide of Davidson-type oxidized zirconiumcomposition, and (b) an oxide of the present invention. The bright whiteareas in image (b) are secondary phase.

FIG. 16 shows the ratio of atomic concentration of oxygen to atomicconcentration of zirconium of Davidson-type oxidized zirconiumcomposition and that disclosed in this invention. The depth profileanalysis was carried out using x-ray photoelectron spectroscope (Al kα,take off angle 45°) and an ion gun for sputtering (Ar+, 3 keV, silicasputter rate of 48 angstroms/minute).

FIG. 17 illustrates an error function fit to the micro-hardness indentsin the diffusion hardened zone to estimate the depth of hardening. Thediffusivity values are in cm ²/s and are approximate. Time is in secondsand distance is in microns.

FIG. 18 illustrates the microstructure of (a) as received Zr-2.5Nb barstock, (b) oxidized at 635° C. for 75 minutes and diffusion hardened at585° C. for 10 hours, (c) oxidized at 690° C. for 60 minutes anddiffusion hardened at 685° C. for 20 hours, and (d) oxidized at 635° C.for 75 minutes and diffusion hardened at 750° C. for 20 hours, and (e)oxidized at 850° C. for 20 minutes and diffusion hardened at 850° C. for22 hours. The samples were polished using standard metallographictechniques and were heat tinted to reveal the grain size.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, “a” or “an” means one or more. Unless otherwiseindicated, the singular contains the plural and the plural contains thesingular.

As used herein, “zirconium alloy” is defined broadly, and includesalloys having at least 5% (w/w) zirconium. The alloys can be ofzirconium, titanium, hafnium and niobium. The alloys can bepolycrystalline or amorphous or single crystals or combinations of same.

As used herein, “ceramic” is defined as a chemical compound of a metal(or a metal constituent in an alloy) and one or more non-metals,including carbon, oxygen, nitrogen, boron, and combinations thereof.While the preferred embodiment of the ceramic of the present inventionis an oxide, the ceramic of the present invention includes oxides,carbides, nitrides, borides, and any combination thereof. As usedherein, “ceramic layer” is defined as a stratum of material consistingof ceramic which forms a part of a greater material. As used herein, theterm “ceramic coating” refers to a surface transformed layer, surfacefilm, surface oxide, nitride, carbide, boride (or combination thereof)present on the alloy or metal substrate.

As used herein, “ceramic-forming species” is defined as oxygen, carbon,nitrogen, boron, and any combination thereof. It is preferable that theceramic-forming species be in the gas phase during the formation of theceramic layer, although it is possible and within the scope of thepresent invention wherein the ceramic-forming species is present in aphase other than the gas phase. One non-limiting example of a non-gasphase embodiment is wherein the ceramic-forming species is in the solidphase in contact with the substrate to which it is to be introduced. Theceramic-forming species, in addition to forming a ceramic, also acts asa diffusion hardening species in the formation of a diffusion zone.

The “diffusion zone” is defined as the zone below the ceramic surface(if a ceramic surface is present) or at the surface itself (if a ceramicsurface is not present) and that comprises a diffusion hardeningspecies. “Diffusion hardening species” is defined as carbon, oxygen,nitrogen, boron, or any combination thereof. The “diffusion hardenedzone” is defined as that portion of the diffusion zone having hardnessat least 1.1 times greater than the substrate hardness.

As used herein, “biocompatible alloy” is defined as the alloycombinations that are currently used in orthopedic industry. Examples ofsuch alloys include cobalt-chromium-molybdenum,titanium-aluminum-vanadium, nickel-titanium and zirconium-niobium. Theother biocompatible alloys that are referred in this invention are thealloys that are made from either zirconium or titanium or tantalum orniobium or hafnium or combination thereof.

As used herein, the term “vacuum” refers to a pressure of less thanabout 10⁻² torr.

Implants comprising Davidson-type oxidized zirconium have been shown toreduce polyethylene wear significantly. This significant reduction inwear is attributed to its ceramic surface. The oxidized zirconiumimplant typically has 4 to 5 micron thick ceramic surface (zirconiumoxide) that is formed by a thermally driven diffusion process in air.Beneath the zirconium oxide is a hard, oxygen-rich diffusion layer ofapproximately 1.5 to 2 microns. The totality of hardened zones (oxideplus diffusion hardened alloy) render the implant resistant tomicroscopic abrasion (third bodies such as bone cement, bone chips,metal debris, etc.) and slightly less resistant to macroscopic impact(surgical instrumentation and from dislocation/subluxation contact withmetallic acetabular shells). However, like all conventional medicalimplant materials, Davidson-type oxidized zirconium implants aresusceptible to damage caused by dislocation and subluxation(macroscopic). Although not intending to be bound by theory, it isbelieved that this susceptibility is due to the relatively smallthickness of the total hardened zones (5 micron oxide plus 1.5 to 2micron diffusion zone) in the Davidson-type oxidized zirconium products.Although Davidson-type oxidized zirconium implants perform better thanmost materials in hard-on-soft applications, the small hardened zone isnot ideal for hard-on-hard bearing applications. The abrasion resistanceof oxidized zirconium and other common implant alloys can be improved byincreasing the depth of totality of the hardened zones. Such hardenedalloys are suitable for articulation against soft polymers (such asUHMWPE, XLPE, polyurethane, etc) and in hard-on-hard bearingapplications against like hardened alloys, against CoCr alloys, ceramics(alumina, silicon nitride, silicon carbide, zirconia, etc), and otherhard materials such as diamond, diamond-like carbon, etc.

FIG. 6 shows four types of hardness profiles obtained on Zr-2.5Nb alloysamples using an embodiment of the method of the present invention. Thefour profiles obtained are Profile 1: uniform function, Profile 2: acombination of uniform function and exponential function, Profile 3: acombination of exponential function and error function, Profile 4: errorfunction. As will be discussed in detail, the resultant shape of thehardness profile was carefully controlled by the oxide thickness,oxidation and vacuum treatment temperatures and time. In this particularexample, the starting oxide thickness was varied by varying oxidationtime at a constant temperature of 635° C. Samples were oxidized for 5minutes, 15 minutes, 30 minutes and 60 minutes respectively. All thesamples were vacuum treated at 685° C. for 10 hours. After vacuumtreatment the four samples produced four different profiles as shown inFIG. 6. The oxide was retained on sample with profile 4 and wascompletely dissolved on samples with profiles 1 to 3. Each of theseprofiles can have a distinct advantage over the other. For example, ifthe oxidation step needs to be repeated after vacuum treatment to formoxide, then Profiles 1 to 3 may produce a high integrity predominantlydefect-free oxide compared to Profile 4. FIG. 7 shows metallographicimages of the oxide formed on samples with different profiles. Thesesamples were oxidized after the vacuum treatment at 635° C. for 1 hourto produce 5 to 6 micron thick oxide. As can be seen, oxide on theProfile 4 is cracked and non-uniform compared to that formed in Profiles1 to 3. This is believed to be caused by lack of plasticity of thediffusion hardened zone that can not accommodate stresses generatedduring re-oxidation. This example illustrates another embodiment of theinvention that will be disclosed. If re-oxidation of the alloy samplesis desired after diffusion hardening process, it is important to obtainan adequate diffusion profile (Profiles 1 to 3). The appropriatediffusion profile ensures a substantially defect-free oxide formationafter the vacuum treatment. The oxidation process is typicallyaccompanied by the volume expansion of the surface (oxide). If thestresses generated during volume expansion are not accommodated in thesubstrate, it can lead to defects such as cracks and pores in the oxide.An example of such defects in the oxide is shown in FIG. 7 (Profile 4).Cracks and pores can compromise integrity of the oxide and may lead tospalling of the oxide. Another type of defect that is anticipated inthis disclosure is the uniformity of the oxide-metal interface. FIG. 7shows an example of wavy interface formed on samples of Profile 3. Thereare few pores and cracks but there are areas where the oxide thicknessis less than 50% of the nominal oxide thickness. Such type of wavyinterface may be unacceptable for a medical implant since there is apotential compromise of the integrity of the oxide.

In a medical implant application, it is desirable that the oxide (orother ceramic layer) formed is substantially defect-free. When the oxideis formed on zirconium alloy substrate, there is expansion of volume asoxygen atoms are added in the zirconium matrix. This volume expansionleads to significant amount of stresses that need to be dissipated. Ifthe substrate underneath is significantly brittle to start with, poresand cracks may form in the oxide to dissipate the stresses. It may alsolead to a wavy interface between the oxide and metal. It sometimes maylead to spalling of the oxide as well. The defects in the oxide can bebroadly classified as pores and cracks. The pores can be circular orelongated and may be on the surface or at the interface. The cracks canbe perpendicular to the oxide metal interface, and/or may be parallel tothe oxide metal interface. Another type of defect that is anticipated inthis disclosure is the wavy oxide metal interface and delaminated orspalled oxide. One object of the present invention is to produce asubstantially defect-free ceramic layer with a thicker diffusionhardened zone. As mentioned previously, following the prior artteachings of Kemp and Davidson, a thicker diffusion zone can be obtainedbut it produces an oxide that is not substantially defect-free. Forexample, FIG. 2( a) shows that the oxide is separated from the oxidemetal interface. FIG. 2( b) shows a crack perpendicular to the oxidemetal interface. FIG. 7 (profile 4) shows oxide with several elongatedpores, and cracks that are parallel to the interface. FIG. 7 (profile 3)shows an example of another type of defect where the oxide metalinterface is wavy. It is the object of this invention to form a ceramiclayer that is substantially free of such defects. The defects in theceramic layer are evaluated on a cross-sectional metallographic sampleat 1000× magnification with field of view of approximately 100×80microns. The substantially defect-free ceramic layer of the presentinvention is characterized by a) average pore diameter smaller than 15%of ceramic layer thickness, b) average crack length parallel to theceramic layer/metal interface to be less than 25% of ceramic layerthickness, (c) average opening width of crack perpendicular to theceramic layer/metal interface to be less than 15% of ceramic layerthickness and (d) the difference between average and minimum ceramiclayer thickness to be less than 50% of the nominal oxide thickness. Itis possible that the all defects described above may appear in one fieldof view or only few of them in one view and all remaining in anotherview. The defect-free ceramic layer of the present invention is definedas that in which above mentioned defects are not seen in at least 3 outof 5 fields of randomly chosen views. The ceramic layer which issubstantially free of such defects is termed as defect-free.

In the present invention, there is medical implant and a method ofproducing the medical implant; the medical implant having a defect-freeceramic layer comprising a secondary phase along with diffusion hardenedzone underneath the ceramic layer. This is accomplished by carefulcontrol of the ceramic formation and diffusion hardening temperatures.In one aspect of this invention, this leads to a preferred profile ofthe hardened zone beneath the ceramic layer. In another aspect of theinvention, the ceramic layer is preferentially retained on the surfaceand is comprised of a secondary phase. In another aspect of invention,an adequate hardness profile is obtained if re-formation of the ceramiclayer is required after diffusion hardening. In another aspect of thepresent invention, the diffusion zone is comprised of a layeredstructure. In another aspect of the present invention, a hardenedmetallic film is formed on the surface of the ceramic layer.

The effect of the hardened zone on damage tolerance was evaluated by aRockwell indent and by carrying out a wear test. FIG. 8 shows backscattered electron images of the indents on Davidson-type oxidizedzirconium composition and that disclosed in this invention. The damagewas produced on a flat disk by indenting the surface with a Rockwellindenter (diamond) with a load of 150 lbf. FIGS. 8( a) and 8(b) showdamage produced on the Davidson-type oxidized zirconium composition. Itshould be noted that applied stress is much greater than that expectedin the body. The indent has caused the oxide to crack in circumferentialand in radial direction. The bright area in the center is exposedZr-2.5Nb substrate. The grayish area is oxide. Due to the amount ofstrain induced during indentation, oxide at the edges of the indent iscracked and removed along with the substrate material. FIGS. 8( c) and8(d) show damage produced on one of the compositions of the presentinvention. This sample was oxidized at 635° C. for 75 minutes and thendiffusion hardened at 685° C. for 10 hours at a pressure of 10⁻⁴ torr.The oxide (approximately 4 micron thick) was retained on this sample.The hardened metallic layer formed on the surface was removed by diamondpolishing before the test. The total hardened zone of this sample is 20to 25 microns. The damage on this sample is significantly less for thenew composition than it is for the Davidson-type oxidized zirconiumcomposition. Less amount of substrate Zr-2.5Nb is exposed at the center.The ceramic layer is not removed along the edges of the sample. Althoughthe Davidson-type oxidized zirconium composition was a great advance formedical implants and continues to be superior to other conventionalmedical materials, this example shows the marked improvement in thedamage resistance obtained over the Davidson-type oxidized zirconiumcompositions. FIG. 9 shows results of a wear study when a composition ofthe present invention (in this case, a ceramic oxide) was articulatedagainst itself in a pin on disk test. The test was run on a pin on disktester at an applied load of 10 N for 1 Mcycle. Load was increased to50N at approximately 0.5 Mcycles. Lactated ringer's solution was used asthe test medium. The disks were flat and the pins had 100 mm radius. Thedisks and pins of Zr-2.5Nb were oxidized at 635° C. for 120 minutes andthen diffusion hardened at 685° C. for 10 hours. The oxide(approximately 7 microns) was retained after diffusion hardeningprocess. The metallic layer and part of the oxide was removed by diamondpolishing before the test. The pins were used in as diffusion hardenedcondition and comprised of metallic hardened layer over the oxide andthe layered diffusion zone underneath the oxide. A comparison was alsomade to the current standard of hard-on-hard bearings, high carbon castCoCr. The wear of the new composition was approximately 34 times lessthan that of CoCr against CoCr couple. The pin-on disk test does nottake into account the geometrical constraints encountered in a hip, kneeor spinal joint. Another object of the present invention is to alsoaccount for the geometrical aspects of the joint. It is well-known thatwear in a hard-on-hard hip joint is biphasic. The first phase of wear isa run-in wear and the second phase is steady-state wear. In the run-inphase, the asperities of the mating components wear out. After therunning in wear, based on the component geometry and the stiffness ofthe components, a fluid film is formed between the mating components.This is typically termed as steady-state wear. The steady-state wear istypically less than run-in wear. One of the approaches to reduce therun-in and steady-state wear is to use metal-ceramic articulation astaught by Fisher et al (U.S. Patent Application 2005/0033442) andKhandkar et al (U.S. Pat. No. 6,881,229). Although this will reducemetal-ion release, the fracture risk of the ceramic component stillprevails.

In another approach, Lippincott and Medley (U.S. Pat. No. 6,059,830)teach applying geometrical constraints to the mating hip components. The'830 patent teaches the use of components such that the radiusdifference of the mating components is less than 50 microns. This smalldifference in radius will promote thicker fluid film formation and thusreduced wear of mating metallic components. The disadvantage of thismethod is that a sophisticated manufacturing set-up is required toproduce components with such tight tolerances. The inventors of thepresent invention have found that such a demanding manufacturingapproach is not necessary. A thicker fluid film can also be formed byusing lower elastic modulus (E) alloys such as, for example, Zr and/orTi alloys (having, for example, E<120 GPa), instead of using higherelastic modulus alloys such as CoCr alloys (having, for example, Etypically greater than 200 GPa). This allows for other metal and metalalloy systems (other than zirconium and/or titanium) to be used in thepresent invention as a substrate of the medical implant when the elasticmodulus of such metal and metal alloy systems is less than 200 GPa. Inone aspect of invention, the radial difference between the matingcomponents of the present invention is kept above 50 microns and basedon the radius of the component used can be as high as 150 microns orgreater.

Although most of the discussion relates to oxidize ceramic compositions,the present invention encompasses both ceramic compositions also (theseinclude oxides, nitrides, borides, carbides, and any combination of theforegoing). The ceramic composition of the present invention has asubstantially thicker diffusion hardened zone than the Davidson-typeoxidized zirconium compositions. The diffusion zone of the compositionsof the present invention has a layered structure unlike the diffusionzone of the Davidson-type compositions of the prior art. The thicknessof the diffusion zone is at least equal to that of the ceramic layerformed on the surface of such an implant. This is accomplished byapplication of specific processes and the formation of a novelcomposition. FIG. 10 shows a comparison of oxygen concentration profileof the diffusion zone of Davidson-type oxidized zirconium compositionand that of a composition of the present invention. The oxygen richdiffusion zone in Davidson-type oxidized zirconium composition isbetween 1 to 2 microns. The oxygen concentration at the interface(between the oxide and diffusion hardened zone) is approximately equalto the solubility limit of oxygen in alpha zirconium which isapproximately 9% (w/w) or 30 atomic %. In the compositions shown in FIG.10, the oxygen rich diffusion zone is greater than 15 microns. FIG. 11shows a comparison of micro-hardness profiles of the Davidson-typeoxidized zirconium composition to one of the compositions of the presentinvention. The depth of hardening is significantly greater in thecomposition of the present invention compared to the Davidson-typecomposition. Two profiles (585° C.—10 hours and 685° C.—10 hours) appearto follow an exponential, error function type of profile. Samplesdiffusion hardened at 750° C. appear to follow a combination of uniformand error/exponential function. These combinations of differentfunctions appear to originate from the layered microstructure of thediffusion hardened zone and are related to the thickness of oxideretained on the surface. FIG. 12 shows anodized metallographiccross-sectional images of the Davidson-type oxidized zirconiumcompositions and new diffusion hardened compositions of the presentinvention. FIG. 12( a) shows the Davidson-type oxidized zirconiumcomposition. It is characterized by the oxide and a very smallunresolved diffusion hardened zone. The layered structure of thediffusion hardened zone of the present invention is absent in theDavidson-type composition. The total hardening depth of this compositionis approximately 7 microns. FIG. 12( b) illustrates the composition ofthe present invention. This particular composition has zirconium oxideand the diffusion zone that is characterized by at least two layers. Thefirst layer is beneath the oxide and the second layer is beneath thefirst layer. Thickness of the second layer is less than the first layer.The total hardening depth is approximately 12 microns.

FIG. 12( c) shows another embodiment of the composition of the presentinvention. This particular composition has zirconium oxide on thesurface and the diffusion zone that is characterized by at least threelayers. The first layer is beneath the oxide, the second layer isbeneath the first layer and the third layer is beneath the second layer.The thickness of the first layer is greater than the second layer andthickness of second layer is greater than the third layer. The totalhardening depth is approximately 30 microns. FIG. 12( d) shows anotherembodiment of the composition of the present invention. This particularcomposition has zirconium oxide layer thickness which is less than 0.2microns and difficult to resolve under an optical microscope. The firstlayer is beneath the thin oxide. The second layer is beneath the firstlayer and the third layer is beneath the second layer. All the layers inthis particular composition have similar thicknesses. In one aspect ofthis invention, the oxide is preferentially retained on the surface(FIGS. 12( b), 12(c) and 12(d)) during the vacuum treatment. Thisparticular aspect leads to further distinctions between theDavidson-type oxidized zirconium composition and that of the presentinvention. The monoclinic content of the composition disclosed in thisinvention is typically greater than 96% (v/v). The typical monocliniccontent of the Davidson-type oxidized zirconium composition is less than93% (v/v) (V. Benezra, S. Mangin, M. Treska, M. Spector, G. Hunter andL. Hobbs, Materials Research Society Symposium Proceedings, Volume 550,Symposium held Nov. 30-Dec. 1, 1998, Boston, Massachusetts, USA, L.Hobbs, V. Benezra Rosen, S. Mangin, M. Treska and G. Hunter,International Journal of Applied Ceramic Technology, 2(3), 221-246, 2005and Sprague, J., Aldinger, P., Tsai, S., Hunter, G., Thomas, R., andSalehi, A., “Mechanical behavior of zirconia, alumina, and oxidizedzirconium modular heads”, ISTA 2003, vol. 2, S. Brown, I. C. Clarke, andA. Gustafson (eds.), International Society for Technology inArthroplasty, Birmingham, Ala., 2003.). FIG. 13 shows the X-raydiffraction pattern of a Davidson-type oxidized zirconium and the X-raydiffraction pattern of the composition of the present invention. Thereflection of tetragonal phase is prominently present in Davidson-typecomposition whereas it is negligibly small in the composition disclosedin this invention. The typical monoclinic content of the composition ofthe present invention is equal to or greater than 96% (see Table 1). TheDavidson-type oxidized zirconium was produced by oxidizing at 635° C.for 75 minutes. One embodiment of the composition of the presentinvention was produced by oxidizing at 635° C. for 150 minutes andvacuum diffusion hardening at 685° C. for 10 hours at 10⁻⁴ torr. Theoxide was retained at the end of the process. The metallic hardenedlayer and part of the oxide were removed by mechanical polishing priorto x-ray diffraction analysis. The remaining phases are most likelycubic or tetragonal or amorphous or a combination thereof.

TABLE 1 Percent monoclinic content analysis of Davidson-type oxidizedzirconium and one of the compositions disclosed in this invention.Davidson-type oxidized Composition of the Sample zirconium presentinvention 1 84 ± 2 97 ± 1 2 82 ± 1 98 ± 2 3 82 ± 1 98 ± 1 Hobbs et. al.<93 — Sprague et. al. 88 ± 3 —

At room temperature, zirconium oxide is stable as a monoclinic phase. Itis believed that the prolonged treatment at elevated temperature led tothis distinction between the two compositions. Another distinction incomposition between the Davidson-type composition and that of thepresent invention is the structure of ceramic layer. In theDavidson-type oxidized composition a distinct secondary phase is seen inthe vicinity of the interface between the oxide and the substrate. Thissecondary phase extends from the substrate through the interface intothe oxide. This phase penetrates to an extent of approximately ¾^(th) orless of the oxide thickness. Only in rare occasions, this phase is seenat the outer surface of the Davidson-type oxidized zirconiumcomposition. In contrast to the Davidson-type oxidized composition, thecomposition of present invention shows this distinct secondary phasethrough the entire thickness of the ceramic layer. In the Davidson-typeoxidized composition, this distinct secondary phase is visible only upto a certain depth in the oxide from the oxide-metal interface. FIG. 14shows scanning electron microscope images of the cross-section showingoxide of Davidson-type oxidized zirconium composition and that of thepresent invention. In the Davidson-type composition of zirconium oxide,the secondary phase is present from the oxide/metal interface to at most¾^(th) of the oxide thickness (FIGS. 14( a) and 14(b)). Occasionally itis seen on the surface of the oxide. This is consistent with thatreported by Benezra et. al. and Hobbs et. al. Whereas, in thecomposition of the present invention, secondary phase is present throughthe entire thickness of the oxide (FIGS. 14( c) and 14(d)). Although notintending to be bound by theory, it is believed that this is due to theprolonged vacuum treatment. FIG. 15 shows scanning electron microscopeimages of the surface of the oxide. No secondary phase is seen onsurface of Davidson-type oxidized zirconium composition (FIG. 15( a)).The composition disclosed in this invention clearly shows presence ofsecondary phase on the surface (FIG. 15( b)). It should be noted thatthis distinction is visible when the ceramic layer is retained on thesurface at the end of the vacuum treatment. If re-formation of theceramic layer is carried out after the diffusion treatment secondaryphase may not be present up to the surface. As stated previously,underneath the ceramic layer is a layered structure of diffusion zone.The Zr-2.5Nb is comprised of two phases, alpha (hexagonal) and beta(cubic). The diffusion zone is predominantly alpha phase (hexagonal). Aminor amount of beta (cubic) phase (less than 7% (v/v)) can be presentin the first layer of diffusion zone. The first layer is predominantlyalpha phase and the volume fraction of beta phase gradually increases inthe diffusion layer towards the substrate. If the zirconium alloy ispredominantly single phase (alpha) then the beta phase in the diffusionzone will be significantly less than it is in the substrate.

In one embodiment of the composition of the present invention, when theceramic layer is retained on the surface during the vacuum treatment,based on the pressure and temperature used, metallic hardened surface isformed on the ceramic layer along with the diffusion zone formedunderneath the ceramic layer. This metallic hardened zone is the resultof the reaction at the ceramic layer/vacuum interface. FIG. 16 showsratio of atomic concentration of oxygen to atomic concentration ofzirconium (O/Zr) of Davidson-type oxidized zirconium composition and oneof the compositions disclosed in this invention. If the organiccontamination on the surface is ignored, the O/Zr ratio of Davidson-typecomposition starts at 1.4 and seems to be constant through the thicknessevaluated in this analysis. For the new composition disclosed in thisinvention, O/Zr ratio starts at 0.3 and gradually increases to 1.2 inthe oxide. The top 0.2 micron layer shown in the image is the metallichardened layer described in this invention. This layer may or may not beretained on the final medical implant. Below this metallic hardenedlayer is the ceramic layer (in this case, an oxide) and below the oxideis the layered structure of diffusion zone. The composition of the oxidedisclosed in this invention appears to be slightly more oxygen deficientcompared to the Davidson-type composition. It should be noted that thisanalysis was carried out using x-ray photoelectron spectroscope (XPS).The surface was analyzed while being removed (sputtered) using an iongun. The depths are approximate and are based on the sputtering rate ofsilicon dioxide. XPS is sensitive to surface organic contamination(carbon-oxygen) and hence shows higher O/Zr ratio on the surface. It isreasonable to surmise that the top few layers (0.03 micron) are thesurface contaminants.

The diffusion-hardened ceramic layers of this invention are produced byemploying three processes. All processes can be performed in a single ormultiple steps. The processes are (1) ceramic layer formation (i.e.,oxidation, nitridation, boridation, carburization, or any combinationthereof), (2) diffusion hardening, and optionally, (3) ceramic layerformation. If ceramic layer is retained on the surface during thediffusion hardening, process 1 and 2 may be sufficient. If the finalapplication is such that a ceramic layer is not required on the surface,temperature and time are chosen in such a way that process 2 willdissolve the ceramic layer completely. Alternatively, the surfaceceramic layer may be removed by mechanical, chemical or electrochemicalmeans. When the ceramic layer is retained on the surface it may form ametallic hardened layer on the oxide. This film may or may not beremoved for the final product. If the ceramic layer is completelydissolved into the substrate and reformation of the ceramic layer isdesired then a diffusion profile is obtained which will produce a highintegrity and defect-free ceramic layer during the ceramic layerformation process. This diffusion profile can be an exponentialfunction, an error function, a uniform, or any sequential combinationthereof (FIG. 6, Profiles 1 to 3). It should be noted that some of thesefunctions may also be attributed to be linear or higher orderpolynomials. It should be noted that the combination of diffusionprofile and retained oxide is obtained through careful control of time,temperature and pressure during ceramic layer formation process anddiffusion hardening process.

For Zr-Nb-based alloys, the damage-resistant implant is such that it hasceramic layer thicknesses ranging from 0.1 to 25 microns and a diffusionhardened zone (DHZ) significantly greater than 2 micron. The DHZ can be70 micron or greater. The DHZ is defined as the region which hashardness at least 1.1 times of the substrate hardness.

There are three general methods to produce the composition of thepresent invention. It should be understood that variations by way ofsubstitutions and alterations from these general methods which do notdepart from the spirit and scope of the invention are understood to bewithin the scope of the invention. In this way, the general methodsdescribed below are merely illustrative and not exhaustive. In each ofthe examples provided, the ceramic layer formation steps are oxidationsteps (thereby producing ceramic oxides). It should be understood thatthese steps are not limited to oxidation and the formation of ceramicoxides; in addition to or in the alternative of, an oxidation step, onemay use a carburization step, a boridation step, a nitridation step, orany combination thereof (including a combination of oxidation and one ormore other steps). In this way, the ceramic so produced can be any oneor, or a combination of an oxide, nitride, boride, and carbide.

Method A, the ceramic oxide and a thick diffusion hardened zone on thedamage-resistant surface is formed by carrying the following processsteps:

-   -   1. Ceramic Layer Formation. Oxidation by diffusion of oxygen in        air at temperature less than 700° C. for times greater than 5        minutes. The oxidation time can be approximated by parabolic        relationship of time and oxide thickness (x²=kt, where k is a        constant, t is time and x is thickness of the oxide. k is        function of temperature). In certain cases a cubic or higher        order polynomial relationship may also be employed.    -   2. Diffusion Hardening. Treating under vacuum or under inert gas        the above said implant at a temperature range from 500° C. to        1000° C. for a period of greater than 1 hour in vacuum at a        pressure less than atmospheric (typically less than 10⁻² torr).        This step either partially or completely dissolves the oxide        layer formed in step 1. The oxygen atoms thus released are        driven deeper into the alloy substrate, hardening the material.        The time and temperature required to obtain a certain diffusion        hardening depth can be estimated from an error-function        relationship. Hardness at depth d (Hd) is given by:

$H_{d} = {H_{i} + {\left( {H_{i} - H_{o}} \right){{erf}\left\lbrack \frac{- d}{2\sqrt{Dt}} \right\rbrack}}}$

-   -    where, H_(i) is the hardness at the interface, H_(o) is the        hardness of the bulk substrate significantly away from the        diffusion zone, D is diffusivity of diffusing species at the        vacuum treatment temperature and t is time of treatment. “erf”        is the error function. All the parameters should be used in        consistent units. The diffusivity of oxygen can be obtained from        the published literature. In this relationship, it is assumed        that the hardness is directly proportional to oxygen at all        concentration levels, and diffusivity of diffusing specie is        independent of concentration. This is a simplistic view to        approximately estimate the dept of hardening. Those skilled in        the art can hypothesize different relationships of diffusing        specie and the hardness and may obtain a different relationship        but the overall shape and profile will follow that described in        this invention. As an example, if the relationship is        exponential or combination of uniform and exponential or error        function, then the depth estimation will be inaccurate using the        above said equation. An example of same is shown in FIG. 17.        Sample in FIG. 17( a) was oxidized at 635° C. for 75 minutes and        then subsequently diffusion hardened at 685° C. for 10 hrs. The        oxide was retained on this sample after the vacuum diffusion        treatment. An error function fit seems to be adequate. Sample in        FIG. 17( b) was oxidized at 635° C. for 75 minutes and then was        diffusion hardened at 750° C. for 20 hrs. A very small fraction        of oxide was retained on the surface. An error function fit is        not adequate for this particular sample. It seems that        sequential combination of error function and uniform fit may        model the hardening behavior.    -   3. Optional Ceramic Layer Formation. Optionally, the implant is        subsequently oxidized again at temperature less than 700° C. in        air for times greater than 5 minutes. As shown in FIGS. 6 and 7,        a suitable hardness profile prior to oxidation is essential to        produce high integrity substantially defect-free oxide.

Ceramic layer formation and diffusion hardening at temperatures lessthan 700° C. helps to preserve the microstructure of the substrate. FIG.18 shows the substrate microstructure of samples diffusion hardened atdifferent temperatures. The grain size of the as-received bar stock isless than 1 micron (FIG. 18( a)). The microstructure shows orientationof the grains along the rolling direction. The grain size of the samplesdiffusion hardened at 585° C. show slight coarsening (FIG. 18( b)). Theorientation of the microstructure is still preserved. FIG. 18( c) showsgrain size of the sample diffusion hardened at 685° C. for 20 hours. Thegrain size shows noticeable coarsening compared to as-received barstock. The orientation of the grains is still present. FIG. 18( d) showsmicrostructure of samples diffusion hardened at 750° C. for 20 hours.There is significant coarsening of the grains. The orientation of thegrains has disappeared and the grains have become equiaxed. The size ofthe grains is greater than 1 micron. FIG. 18( e) shows microstructure ofsamples diffusion hardened at 850° C. for 22 hours. Significantcoarsening of the grains can be seen. The size of the grains is above 10microns. Alternatively, the second step may be carried out at atemperature and time such that part of the oxide formed in step 1 isretained on the surface. The third step of ceramic layer formation maybe altogether eliminated if any remaining ceramic layer is sufficient.It should be noted that when the ceramic layer is retained on thesurface, a thin metallic hardened film forms on the surface. Thecomposition of the film is shown FIG. 16. This film may be retained onthe surface or can be polished by mechanical, chemical orelectrochemical means if desired. Alternatively, the second step ofdiffusion hardening is carried out in an inert atmosphere such ascomposed of argon (or other inert gas) with partial pressure of oxygen(or other diffusion hardening species) in the system typically less than0.2×10⁻² torr and temperature range from 500° C. to greater than 800° C.Alternatively, if reformation of ceramic layer is desired as a thirdstep, an adequate diffusion profile is obtained to produce a highintegrity, predominantly defect-free ceramic layer (FIGS. 6 and 7).

In Method B, the ceramic oxide and a thick diffusion hardened zone onthe damage-resistant surface is formed by carrying the following processsteps:

-   -   1. Ceramic Layer Formation. Oxidation by diffusion of oxygen in        air at temperature range of 500° C. to 1000° C. (preferably less        than 700° C.) for times greater than 5 minutes. The oxidation        time can be approximated by parabolic relationship of time and        oxide thickness (x²=kt, where k is a constant, t is time and x        is thickness of the oxide. k is function of temperature). In        certain cases a cubic or higher order polynomial relationship        may also be employed.    -   2. Diffusion Hardening. Treating under vacuum (i.e., pressure        less than about 10⁻² torr) or under inert gas the above said        implant at a temperature of less than 700° C. The exact        temperature and time are chosen such that a desired oxide        thickness remains on the surface after the vacuum treatment step        is completed. This step likely partially consumes the oxide        layer formed in step 1. The oxygen atoms thus released are        driven deeper into the alloy substrate, hardening the material.        The diffusion hardening depth can be estimated from an        error-function relationship. Hardness at depth d (Hd) is given        by:

$H_{d} = {H_{i} + {\left( {H_{i} - H_{o}} \right){{erf}\left\lbrack \frac{- d}{2\sqrt{Dt}} \right\rbrack}}}$

-   -    where, H_(i) is the hardness at the interface, H_(o) is the        hardness of the bulk substrate significantly away from the        diffusion zone, D is diffusivity of diffusing species and t is        time of treatment. “erf” is the error function. All the        parameters should be used in consistent units. The diffusivity        of oxygen can be obtained from the published literature. In this        relationship, it is assumed that the hardness is directly        proportional to oxygen at all concentration levels, and        diffusivity of diffusing specie is independent of concentration.        This is a simplistic view to approximately estimate the dept of        the hardening. Those skilled in the art can hypothesize        different relationships of diffusing specie and the hardness and        may obtain a different relationship but the overall shape and        profile will follow that described in this invention. It should        be noted that this relationship is an approximate way to        estimate the depth of hardening. If the profile is exponential        or combination of uniform and exponential or error function,        then the depth estimation using the equation above will be        inaccurate. An example of same is shown in FIG. 17. Sample shown        in FIG. 17( a) was oxidized at 635° C. for 75 minutes and then        subsequently diffusion hardened at 685° C. for 10 hours. Oxide        was retained on the surface. An error function fit seems to be        adequate. Sample in FIG. 17( b) was oxidized at 635° C. for 75        minutes and then was diffusion hardened at 750° C. for 20 hours.        A small fraction of oxide was retained on the surface. An error        function fit is not adequate for this particular sample. It        seems that sequential combination of error function and uniform        fit may model the hardening behavior.    -   3. Optional Ceramic Layer Formation. Optionally, the implant is        subsequently oxidized again at temperature less than 700° C. in        air for times greater than 5 minutes. As shown in FIGS. 6 and 7,        a suitable hardness profile prior to oxidation is essential to        produce high integrity substantially defect-free oxide.

By vacuum (or inert gas) treating at lower temperatures a desired oxidethickness remains on the surface and promotes the preservation of themicrostructure of the substrate. FIG. 18 shows the substratemicrostructure of samples diffusion hardened at different temperatures.The grain size of the as-received bar stock is less than 1 micron (FIG.18( a)). The microstructure shows orientation of the grains along therolling direction. The grain size of the samples diffusion hardened at585° C. show slight coarsening (FIG. 18( b)). The orientation of themicrostructure is still preserved. FIG. 18( c) shows grain size of thesample diffusion hardened at 685° C. for 20 hours. The grain size showsnoticeable coarsening compared to as-received bar stock. The orientationof the grains is still present. FIG. 18( d) shows microstructure ofsamples diffusion hardened at 750° C. for 20 hours. There is significantcoarsening of the grains. The orientation of the grains has disappearedand the grains have become equiaxed. The size of the grains is greaterthan 1 micron. FIG. 18( e) shows microstructure of samples diffusionhardened at 850° C. for 22 hours. Significant coarsening of the grainscan be seen. The size of the grains is above 10 microns. Alternatively,if re-formation of ceramic layer is desired as a third step, an adequatediffusion profile is obtained to produce a high integrity, predominantlydefect-free ceramic layer (FIGS. 6 and 7).

In Method C, the ceramic oxide and a thick diffusion hardened zone onthe damage-resistant surface is formed by carrying the following processsteps:

-   -   1. Ceramic Layer Formation. Oxidation by diffusion of oxygen in        air at temperature less than 700° C. for times greater than 5        minutes. The oxidation time can be decided based on the        parabolic relationship of time and oxide thickness (x²=kt, where        k is a constant, t is time and x is thickness of the oxide. k is        function of temperature). In certain cases a cubic relationship        may also be employed.    -   2. Diffusion Hardening. Treating under vacuum (i.e., pressure        less than about 10⁻² torr) or under inert gas the above said        implant at a temperature of less than 700° C. The exact        temperature and time is chosen such that a desired oxide        thickness remains on the surface after the vacuum treatment step        is completed. This step likely partially consumes the oxide        layer formed in step 1. The oxygen atoms thus released are        driven deeper into the alloy substrate, hardening the material.        The time and temperature required to obtain a certain diffusion        hardening depth can be estimated from an error-function        relationship. Hardness at depth d (H_(d)) is given by:

$H_{d} = {H_{i} + {\left( {H_{i} - H_{o}} \right){{erf}\left\lbrack \frac{- d}{2\sqrt{Dt}} \right\rbrack}}}$

-   -    where, H_(i) is the hardness at the interface, H_(o) is the        hardness of the bulk substrate significantly away from the        diffusion zone, D is diffusivity of diffusing species and t is        time of treatment. “erf” is the error function. All parameters        should be used in consistent units. The diffusivity of oxygen        can be obtained from the published literature. In this        relationship, it is assumed that the hardness is directly        proportional to oxygen at all concentration levels, and        diffusivity of diffusing specie is independent of concentration.        This is a simplistic view to approximately estimate the depth of        hardening. As an example, if the relationship is exponential or        combination of uniform and exponential or error function, then        the depth estimation will be inaccurate. An example of same is        shown in FIG. 17. Sample in FIG. 17( a) was oxidized at 635° C.        for 75 minutes and then subsequently diffusion hardened at        685° C. for 10 hours. Oxide was retained on the surface. An        error function fit seems to be adequate. Sample in FIG. 17( b)        was oxidized at 635° C. for 75 minutes and then was diffusion        hardened at 750° C. for 20 hours. A small fraction of oxide was        retained on the surface. An error function fit is not adequate        for this particular sample. It seems that a sequential        combination of error function and uniform fit may model the        hardening behavior.    -   3. Optional Ceramic Layer Formation. Optionally, the implant is        subsequently oxidized again at temperature less than 700° C. in        air for times greater than 5 minutes. As shown in FIGS. 6 and 7,        a suitable hardness profile prior to oxidation is essential to        produce high integrity, substantially defect-free oxide.

By performing the ceramic layer formation and diffusion hardening(vacuum or inert gas treatment) steps at lower temperatures preservationof the microstructure of the substrate is achieved and a desired ceramiclayer thickness remains on the surface as shown in FIGS. 12 and 18. Thecombination of the ceramic layer formation and diffusion hardening stepsdescribed results in a significantly thicker diffusion hardened zone(greater than 2 microns and preferably greater than 5 microns) incomparison to Davidson-type diffusion hardened oxide and/or nitridecompositions. Additionally, the totality of the ceramic layer and thediffusion hardened zone is 5 microns or greater. These properties resultin a more damage resistant and wear resistant surface, among otheradvantages. The properties of the new composition makes it applicable tohard-on-hard medical implant applications. Non-limiting examples of suchinclude knee and hip prostheses having one surface of the newcomposition articulating against another surface of the new composition.

It should be understood that the temperature and time parameters can bevaried from those provided above, particularly in the case of differentsubstrate compositions. Additionally, the processes may be carried outin a controlled atmosphere. Illustrative but non-limiting examples of acontrolled atmosphere include, controlled oxygen and nitrogen partialpressure, oxygen plasma, in the presence of water gas reactions, in thepresence of reactive gases such as oxygen and ozone in the presence ofinert gases such as argon and nitrogen, in the presence of oxidizing orreducing salts, in the presence of glasses etc. Examples of inert gasesinclude nitrogen, argon, etc. Examples of reactive gases includehydrogen, methane, other hydrocarbons, etc. Other controlled atmosphereconditions, known to those of skill in the art are also included. Thegoal is to form the composition under conditions that do notsignificantly change the microstructure of the substrate alloy.

Alternatively, the process of ceramic layer formation and diffusionhardening can be carried out in an atmosphere that is lean in oxygen (orother ceramic forming species) content (e.g., partial pressure of oxygenless than 0.05 bar). Alternatively, the process can be carried out in asingle step comprising of all the above steps in one process.Alternatively, the process can be carried out in ozone atmosphere or anatmosphere whose oxidation potential is controlled by water-gas reactionsuch as CO₂+H₂═H₂O+CO or using controlled moisture in an inert gasessuch as but not limited to helium, nitrogen, argon and krypton.

Alternatively, the ceramic layer formation and diffusion hardening canbe carried out in two steps that do not change microstructure of thesubstrate alloy significantly. The process of ceramic layer formationand diffusion hardening can be carried out in a two step process. In thefirst step, the alloy is treated with ceramic forming species at atemperature above 700° C. for a period of greater than 12 hours thatforms a thicker diffusion zone along with a cracked ceramic layer or thealloy is diffusion hardened as described in methods A, B and C. In asecond step, the ceramic layer or part of the diffusion zone is removedby mechanical, chemical or electrochemical means and the alloy issubsequently treated to form a ceramic layer at a lower temperature andtime to form an adherent ceramic layer with an already formed diffusionzone and thus producing the damaged resistant implant.

Alternatively, the substrate material is first diffusion hardened usinga lean concentration of diffusion hardening species and then a ceramiclayer is formed (using a more concentrated dose of ceramic-formingspecies to form the ceramic layer).

A two step process can be used. In the first step the material isdiffusion-hardened (oxygen, carbon, boron, or nitrogen) in controlledconditions in which the partial pressure of the hardening species arelean enough not to form stable ceramic compounds with the alloy. Thediffusion zones can be controlled as described above. This is followedby oxidation, carburization, nitridation, borization or any combinationthereof as described above.

The damage-resistant implant is produced by forming the ceramic layer ata temperature preferably ranging from 500° C. to greater than 1000° C.for a time preferably ranging from 5 minutes to greater than 6 hours. Itis preferred that the ceramic formation temperature be under 700° C. topromote preservation of the substrate microstructure. The time andtemperature may be determined from the Arrhenius and parabolicrelationship amongst the ceramic layer thickness, diffusion-hardenedzone thickness, and temperature. Vacuum or inert gas treatment(diffusion hardening) is preferably performed at a temperaturepreferably ranging from 500° C. to greater than 1000° C. for a timepreferably ranging from 15 minutes to greater than 30 hours. It ispreferred that the diffusion hardening treatment temperature be under700° C. to preferentially preserve any of the ceramic oxide formed instep 1 and also to promote preservation of the substrate microstructure.An optional step of reformation of ceramic layer may be performed afterthe initial ceramic layer formation step if additional ceramic layergrowth is desired.

The resulting surface composition can be subject to a variety of surfacepreparation techniques after the step of diffusion-hardening to form theadherent oxide. Such techniques include, but are not limited to, thosetechniques known in the art to be applicable to diffusion-hardenedsurfaces. It is expected that other, more rigorous techniques areapplicable to the composition of the present invention due to itsgreater degree of damage resistance.

In the composition used in the medical implant of the present invention,the totality of the thickness of the ceramic layer and the diffusionhardened zone is greater than 5 microns, and preferably greater than 10microns. Because the ceramic layer may or may not be present (it canrange in thickness from 0 to 25 microns), this requirement may be met bya diffusion hardened zone of a thickness of greater than 5 microns (andpreferably greater than 10 microns) with no ceramic layer above it or aninfinitesimally small ceramic layer above it. Where both layers arepresent, the ceramic layer is on the surface and is above the diffusionhardened zone. While the diffusion hardened zone is one of the twoaforementioned layers, the diffusion hardened zone itself consists of atleast two distinct layers layer (visible by metallographic analysis).The first layer of the diffusion hardened zone has a relatively highconcentration of diffusion hardening species (higher than that of thebulk substrate zirconium or zirconium alloy) and may be saturated withthe diffusion hardening species. The zirconium in the first layer ispredominantly alpha phase zirconium (the first layer of the diffusionhardened zone is that layer which is closest to the ceramic layer, or,where the ceramic layer is absent, the first layer is that layer whichis nearest to the surface of the composition). The second layer is belowthe first layer and has a lower content of diffusion hardening speciesthan the first layer. The diffusion hardened zone has a diffusionhardening species concentration profile such that, in one or morecross-sections of the diffusion hardened zone, the concentration ofdiffusion hardening species decreases as either an error function, anexponential function, a near uniform distribution, or sequentialcombinations thereof. Where combinations of functional profiles arereferred to, it should be understood that such combinations aresequential combinations and do not refer to the superposition of thevarious functional profiles. Where the diffusion hardened layer is verythick due to the use of long formation times, the distribution mayapproach a uniform distribution in at least some sections of thediffusion hardened zone.

The layered structure of the diffusion hardened zone can be detected bymetallographic analytical techniques known to those of ordinary skill inthe art. These include, but are not limited to, anodization, heattinting, x-ray diffraction, Auger spectroscopy, depth profiling, etc.

As described above, the process can be used for an extended period toform a thick cracked ceramic layer and a thick diffusion hardened layer.The cracked ceramic layer can then be removed to retain the diffusionhardened layer for subsequent re-formation of another ceramic layer.

The new composition has application in medical implants of allvarieties. It is expected to be particularly beneficial for use inarticulating implants, such as, but not limited to hip and kneeimplants. Use of such product in other biomedical applications suchspinal devices, small joints, shoulder joints, etc

Resulting medical implants comprising diffusion-hardened ceramic layersof the variety described herein are heated to desired temperatures usingelectric heating, radiative heating, induction heating or usingtechniques such as spark plasma sintering or field assisted sintering.This is accomplished by use of an alloy of Ti, Zr and Nb that is capableof producing thicker totality of hardened zones (ceramic layer and thickdiffusion hardened zone) that is produced by specific processes.

The present composition will be applicable for any and all medicalimplants, but in particular for articulating medical implants such as,but not limited to, hip, knee, shoulder, elbow orthopedic implants, etc.Vertebral implants are also amenable to the present invention. Thepresent invention also finds applicability to any and allnon-articulating medical implants. The improved damage resistance isseen in comparison to the diffusion hardened oxides of theDavidson-type, such as those described in U.S. Pat. No. 5,037,438 toDavidson and U.S. Pat. Nos. 6,447,550; 6,585,772 and pending U.S.application Ser. No. 10/942,464 to Hunter.

Although the present invention and its advantages have been described indetail, it should be understood that various changes, substitutions andalterations can be made herein without departing from the spirit andscope of the invention as defined by the appended claims. Moreover, thescope of the present application is not intended to be limited to theparticular embodiments of the process, machine, manufacture, compositionof matter, means, methods and steps described in the specification. Asone of ordinary skill in the art will readily appreciate from thedisclosure of the present invention, processes, machines, manufacture,compositions of matter, means, methods, or steps, presently existing orlater to be developed that perform substantially the same function orachieve substantially the same result as the corresponding embodimentsdescribed herein may be utilized according to the present invention.Accordingly, the appended claims are intended to include within theirscope such processes, machines, manufacture, compositions of matter,means, methods, or steps.

1. A medical implant comprising: a substrate comprising zirconium orzirconium alloy; a diffusion hardened zone in contact with saidsubstrate, said diffusion hardened zone comprising zirconium orzirconium alloy and a diffusion hardening species, said diffusionhardened zone having a thickness of greater than 2 microns; and, asubstantially defect-free ceramic layer in contact with said diffusionhardened zone and comprising a surface of said medical implant, saidceramic layer ranging in thickness from 0.1 to 25 microns; and, whereinthe total thickness of the ceramic layer and the diffusion hardened zoneis 5 microns or greater.
 2. The medical implant of claim 1, wherein theceramic layer comprises a secondary phase; and, the diffusion hardenedzone has a layered structure comprising at least two distinct layersunder metallographic analysis, the layered structure characterized by: afirst layer directly below the ceramic layer, wherein the first layer ispredominantly alpha phase zirconium; an interface between the firstlayer and the ceramic layer; and; a second layer directly below thefirst layer.
 3. The medical implant of claim 2, wherein the substratefurther comprises titanium, tantalum, hafnium, niobium, and anycombination thereof.
 4. The medical implant of claim 2, wherein saiddiffusion hardening species is selected from the group consisting ofoxygen, nitrogen, boron, carbon, and any combination thereof.
 5. Themedical implant of claim 2, wherein said diffusion hardening speciescomprises oxygen.
 6. The medical implant of claim 5, wherein thediffusion hardened zone has concentration of oxygen which decreases inthe direction of the substrate, said decrease of oxygen concentrationbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof.
 7. The medical implantof claim 5, wherein the ceramic oxide has monoclinic content of greaterthan 93%.
 8. The medical implant of claim 2, wherein said diffusionhardened zone has a hardness profile which is defined by a functionselected from the group consisting of an error function, an exponentialfunction, a near uniform distribution function, and any sequentialcombination thereof.
 9. The medical implant of claim 2, wherein saidfirst layer has a thickness which is greater than or equal to thethickness of said second layer and of any subsequent layers if present.10. The medical implant of claim 2, wherein said diffusion hardened zonehas a thickness of 5 to 70 microns.
 11. The medical implant of claim 2,wherein said diffusion hardened zone has a thickness of 10 to 50microns.
 12. The medical implant of claim 2, wherein said diffusionhardened zone has a thickness of 15 to 30 microns.
 13. The medicalimplant of claim 2, wherein the hardness of the diffusion hardened zoneis at least 10% greater than that of the substrate.
 14. The medicalimplant of claim 2, wherein said medical implant is selected from thegroup consisting of a hip implant, a knee implant, and a spinal implant.15. The medical implant of claim 2, wherein said substrate comprises analloy of zirconium and niobium and has a niobium content of at least 1%(w/w).
 16. The medical implant of claim 15, wherein said substratecomprises an alloy of zirconium and niobium has a niobium content of atleast 10% (w/w).
 17. The medical implant of claim 2, further comprisingan oxygen-containing zirconium alloy overlaying said ceramic oxide ornitride on the surface of said implant, said alloy being in the metallicstate.
 18. A medical implant comprising: a substrate comprisingzirconium or zirconium alloy; a diffusion hardened zone in contact withsaid substrate, said diffusion hardened zone comprising zirconium orzirconium alloy and a diffusion hardening species, said diffusionhardened zone having a thickness of greater than 5 microns; and, whereinthe diffusion hardened zone has a layered structure comprising at leasttwo distinct layers under metallographic analysis, said layeredstructure characterized by: a first layer on a surface of the implant; asecond layer directly below said first layer, wherein said first layeris predominantly alpha phase zirconium; and, said layered structurehaving a concentration of diffusion hardening species which decreases inthe direction of the substrate, said decrease of concentration ofdiffusion hardening species being defined by a function selected fromthe group consisting of an error function, an exponential function, anear uniform distribution function, and any sequential combinationthereof.
 19. The medical implant of claim 18, wherein the substratefurther comprises titanium, tantalum, hafnium, niobium, and anycombination thereof.
 20. The medical implant of claim 18, wherein saiddiffusion hardening species is selected from the group consisting ofoxygen, nitrogen, boron, carbon, and any combination thereof.
 21. Themedical implant of claim 18, wherein said diffusion hardening speciescomprises oxygen.
 22. The medical implant of claim 21, wherein thediffusion hardened zone has a concentration of oxygen which decreases inthe direction of the substrate, said decrease of oxygen concentrationbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof.
 23. The medicalimplant of claim 18, wherein the diffusion hardened zone has a hardnessprofile which is defined by a function selected from the groupconsisting of an error function, an exponential function, a near uniformdistribution function any sequential combination thereof.
 24. Themedical implant of claim 18, wherein said first layer has a thicknesswhich is greater than the thickness of said second layer and of anysubsequent layers if present.
 25. The medical implant of claim 18,wherein said diffusion hardened zone has a thickness of 5 to 70 microns.26. The medical implant of claim 18, wherein said diffusion hardenedzone has a thickness of 10 to 50 microns.
 27. The medical implant ofclaim 18, wherein said diffusion hardened zone has a thickness of 15 to30 microns.
 28. The medical implant of claim 18, wherein the hardness ofthe diffusion hardened zone is at least 10% greater than that of thesubstrate.
 29. The medical implant of claim 18, wherein said medicalimplant is selected from the group consisting of a hip implant, a kneeimplant, and a spinal implant.
 30. The medical implant of claim 18,wherein said substrate comprises an alloy of zirconium and niobium has aniobium content of at least 1% (w/w).
 31. The medical implant of claim30, wherein said substrate comprises an alloy of zirconium, titanium andniobium and has a niobium content of at least 10% (w/w).
 32. A method ofmaking a surface hardened medical implant comprising the steps of:forming said medical implant of zirconium or zirconium alloy; and,further treating said implant by any one of (a), (b), or (c), wherein(a), (b), and (c) are defined as follows: (a) treating said implant inthe presence of ceramic-forming species at a temperature of less than700° C. for greater than 5 minutes; and, thereafter treating saidimplant under vacuum or inert gas at a temperature of from 500° C. to1000° C. for greater than 1 hour; (b) treating said implant in thepresence of ceramic-forming species at a temperature of from 500° C. to1000° C.; and, thereafter treating said implant under vacuum or inertgas at a temperature less than 700° C.; (c) treating said implant in thepresence of ceramic-forming species at a temperature of less than 700°C.; and, thereafter treating said implant under vacuum or inert gas at atemperature less than 700° C.
 33. The method of claim 32, furthercomprising the step of treating said implant in the presence of aceramic-forming species at a temperature less than 700° C. for greaterthan 5 minutes after said step of thereafter treating said implant undervacuum or inert gas.
 34. The method of claim 32, wherein said step ofthereafter treating said implant under vacuum or inert gas is performedat a temperature of 600° C. to 700° C.
 35. The method of claim 32,wherein said step of treating said implant in the presence ofceramic-forming species is performed for between 5 minutes to 12 hours.36. The method of claim 32, wherein said step of thereafter treatingsaid implant under vacuum or inert gas is performed for between 15minutes to 30 hours.
 37. The method of claim 32, wherein said step offorming a medical implant of zirconium or zirconium alloy comprisesforming said medical implant of zirconium alloy having an alloyingelement selected from the group consisting of titanium, tantalum,hafnium, niobium, and any combination thereof.
 38. The method of claim32, wherein said step of forming comprises forming said medical implantof an alloy of zirconium and niobium, said alloy having a niobiumcontent of at least 1% (w/w).
 39. The method of claim 38, wherein saidstep of forming comprises forming said medical implant of an alloy ofzirconium and niobium, said alloy having a niobium content of at least10% (w/w).
 40. The method of claim 32, wherein said step of treatingsaid implant in the presence of ceramic-forming species and said step ofthereafter treating said implant under vacuum or inert gas comprisetreating said implant with a diffusion hardening species selected fromthe group consisting of oxygen, nitrogen, boron, carbon, and anycombination thereof.
 41. A method of making surface hardened medicalimplant comprising steps of: forming said medical implant of zirconiumor zirconium alloy; forming an oxide, carbide, nitride, boride orcombination thereof, on a surface of said implant at a temperature offrom 500° C. to 1000° C. for greater than 2 hours; removing the formedoxide, carbide, nitride, boride, or combination thereof, and, thereafterre-forming an oxide, carbide, nitride, boride, or combination thereof,on a surface of said implant at a temperature of from 500° C. to 1000°C. for greater than 5 minutes.
 42. A method of making surface hardenedmedical implant comprising steps of: forming said medical implant ofzirconium or zirconium alloy; diffusing oxygen or nitrogen into saidimplant at a partial pressure of oxygen or nitrogen of less than 0.05bar and at a temperature ranging from 500° C. to 1000° C. for greaterthan 2 hours; and, thereafter oxidizing or nitriding the implant between500° C. to 1000° C. for greater than 10 minutes.
 43. A method of makinga surface hardened medical implant comprising the steps of: forming saidmedical implant of zirconium or zirconium alloy; oxidizing or nitridingsaid implant at a temperature of from 500° C. to 700° C. to form atleast a 2 micron thick oxide or nitride; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C. toretain at least 0.1 microns oxide, to form at least 0.005 micronsmetallic hardened layer, and to form a diffusion zone having a thicknessof at least 2 microns.
 44. The method of claim 43, wherein the substratefurther comprises titanium, tantalum, niobium, hafnium, and anycombination thereof
 45. The method of claim 43, wherein the oxide ornitride thickness before said step of thereafter treating said implantunder vacuum or inert gas is from 2 to 15 microns.
 46. The method ofclaim 43, wherein the oxide or nitride thickness after said step ofthereafter treating said implant under vacuum or inert gas is from 0.1to 10 microns.
 47. The method of claim 43, wherein the diffusionhardened zone is from 2 to 50 microns.
 48. A medical implant produced bythe process comprising the steps of: forming said medical implant ofzirconium or zirconium alloy; further treating said implant by any oneof (a), (b), or (c), wherein (a), (b), and (c) are defined as follows:(a) treating said implant in the presence of ceramic-forming species ata temperature of less than 700° C. for greater than 5 minutes; and,thereafter treating said implant under vacuum or inert gas at atemperature of from 500° C. to 1000° C. for greater than 1 hour; (b)treating said implant in the presence of ceramic-forming species at atemperature of from 500° C. to 1000° C.; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C.;(c) treating said implant in the presence of ceramic-forming species ata temperature of less than 700° C.; and, thereafter treating saidimplant under vacuum or inert gas at a temperature less than 700° C. 49.A medical implant, comprising: (a) a first implant portion comprisingzirconium or zirconium alloy, said first implant portion having abearing surface; (b) a second implant portion comprising zirconium orzirconium alloy, said second implant portion having bearing surface; (c)wherein the bearing surface of said first implant portion and thebearing surface of said second implant portion each have a size andshape to engage or cooperate with one another; (d) a diffusion hardenedzone in contact with at least a portion of said zirconium or zirconiumalloy, said diffusion hardened zone forming at least a part of thebearing surface of both of said first and second implant portions, saiddiffusion hardened zone comprising zirconium or zirconium alloy and adiffusion hardening species, said diffusion hardened zone having athickness of greater than 2 microns; and, (e) a substantiallydefect-free ceramic layer in contact with said diffusion hardened zoneand comprising a surface of said medical implant, said ceramic layerranging in thickness from 0.1 to 25 microns; wherein the total thicknessof the ceramic layer and the diffusion hardened zone is 5 microns orgreater.
 50. The medical implant of claim 49, wherein the ceramic layercomprises a secondary phase; and, the diffusion hardened zone has alayered structure comprising at least two distinct layers undermetallographic analysis, the layered structure characterized by: a firstlayer directly below the ceramic layer, wherein the first layer ispredominantly alpha phase zirconium; an interface between the firstlayer and the ceramic layer; and; a second layer directly below thefirst layer.
 51. The medical implant of claim 50, wherein the substratefurther comprises titanium, tantalum, hafnium, niobium, and anycombination thereof.
 52. The medical implant of claim 50, wherein saiddiffusion hardening species is selected from the group consisting ofoxygen, nitrogen, boron, carbon, and any combination thereof.
 53. Themedical implant of claim 50, wherein said diffusion hardening speciescomprises oxygen.
 54. The medical implant of claim 53, wherein thediffusion hardened zone has a concentration of oxygen which decreases inthe direction of the substrate, said decrease of oxygen concentrationbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof.
 55. The medicalimplant of claim 53, wherein the ceramic oxide has monoclinic content ofgreater than 93%.
 56. The medical implant of claim 50, wherein thediffusion hardened zone has a hardness profile which is defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function and anysequential combination thereof.
 57. The medical implant of claim 50,wherein said first layer has a thickness which is greater than or equalto the thickness of said second layer and of any subsequent layers ifpresent.
 58. The medical implant of claim 50, wherein said diffusionhardened zone has a thickness of 5 to 70 microns.
 59. The medicalimplant of claim 50, wherein said diffusion hardened zone has athickness of 10 to 50 microns.
 60. The medical implant of claim 50,wherein said diffusion hardened zone has a thickness of 15 to 30microns.
 61. The medical implant of claim 50, wherein the hardness ofthe diffusion hardened zone is at least 10% greater than that of thesubstrate.
 62. The medical implant of claim 50, wherein said medicalimplant said medical implant is selected from the group consisting of ahip implant, a knee implant, and a spinal implant.
 63. The medicalimplant of claim 50, wherein said substrate comprises an alloy ofzirconium and niobium and has a niobium content of at least 1% (w/w).64. The medical implant of claim 63, wherein said substrate comprises analloy of zirconium and niobium has a niobium content of at least 10%(w/w).
 65. The medical implant of claim 50, further comprising anoxygen-containing zirconium alloy overlaying said ceramic oxide ornitride on the surface of said implant, said alloy being in the metallicstate.
 66. A medical implant, comprising: (a) a first implant portioncomprising zirconium or zirconium alloy, said first implant portionhaving a bearing surface; (b) a second implant portion comprisingzirconium or zirconium alloy, said second implant portion having bearingsurface; (c) wherein the bearing surface of said first implant portionand the bearing surface of said second implant portion each have a sizeand shape to engage or cooperate with one another; (d) a diffusionhardened zone in contact with at least a portion of said zirconium orzirconium alloy, said diffusion hardened zone forming at least a part ofthe bearing surface of both of said first and second implant portions,said diffusion hardened zone comprising zirconium or zirconium alloy anda diffusion hardening species, said diffusion hardened zone having athickness of greater than 5 microns; wherein the diffusion hardened zonehas a layered structure comprising at least two distinct layers undermetallographic analysis, said layered structure characterized by: afirst layer on a surface of the implant; a second layer directly belowsaid first layer, wherein said first layer is predominantly alpha phasezirconium; and, said diffusion hardened zone having a concentration ofdiffusion hardening species which decreases in the direction of thesubstrate, said decrease of concentration of diffusion hardening speciesbeing defined by a function selected from the group consisting of anerror function, an exponential function, a near uniform distributionfunction, and any sequential combination thereof.
 67. The medicalimplant of claim 66, wherein the substrate further comprises titanium,tantalum, hafnium, niobium, and any combination thereof.
 68. The medicalimplant of claim 66, wherein said diffusion hardening species isselected from the group consisting of oxygen, nitrogen, boron, carbon,and any combination thereof.
 69. The medical implant of claim 66,wherein said diffusion hardening species comprises oxygen.
 70. Themedical implant of claim 69, wherein diffusion hardened zone has aconcentration of oxygen which decreases in the direction of thesubstrate, said decrease of oxygen concentration being defined by afunction selected from the group consisting of an error function, anexponential function, a near uniform distribution function, and anysequential combination thereof.
 71. The medical implant of claim 66,wherein the diffusion hardened zone has a hardness profile which isdefined by a function selected from the group consisting of an errorfunction, an exponential function, a near uniform distribution functionand any sequential combination thereof.
 72. The medical implant of claim66, wherein said first layer has a thickness which is greater than thethickness of said second layer and of any subsequent layers if present.73. The medical implant of claim 66, wherein said diffusion hardenedzone has a thickness of 5 to 70 microns.
 74. The medical implant ofclaim 66, wherein said diffusion hardened zone has a thickness of 10 to50 microns.
 75. The medical implant of claim 66, wherein said diffusionhardened zone has a thickness of 15 to 30 microns.
 76. The medicalimplant of claim 66, wherein the hardness of the diffusion hardened zoneis at least 10% greater than that of the substrate.
 77. The medicalimplant of claim 66, wherein said medical implant is selected from thegroup consisting of a hip implant, a knee implant, and a spinal implant.78. The medical implant of claim 66, wherein said substrate comprises analloy of zirconium and niobium has a niobium content of at least 1%(w/w).
 79. The medical implant of claim 78, wherein said substratecomprises an alloy of zirconium, titanium and niobium and has a niobiumcontent of at least 10% (w/w).
 80. A medical implant comprising: (a) afirst implant portion, said first implant portion having a bearingsurface; (b) a second implant portion, said second implant portionhaving a bearing surface; (c) wherein the bearing surface of said firstimplant portion and the bearing surface of said second implant portioneach have a size and shape to engage or cooperate with one another; (d)wherein one or both of the two portions of the medical implant comprisesa biocompatible alloy having an elastic modulus less than 200 GPa; and,(e) wherein the difference in radius of the mating portions is greaterthan about 50 microns.
 81. The medical implant of claim 80, wherein oneor both of said first implant portion and said second implant portionfurther comprises: a substrate; a diffusion hardened zone in contactwith said substrate, said diffusion hardened zone comprising a diffusionhardening species, said diffusion hardened zone having a thickness ofgreater than 2 microns; and, a substantially defect-free ceramic layerin contact with said diffusion hardened zone and comprising a surface ofsaid medical implant, said ceramic layer ranging in thickness from 0.1to 25 microns; and, wherein the total thickness of the ceramic layer andthe diffusion hardened zone is 5 microns or greater.
 82. The medicalimplant of claim 81, wherein one or both of said first implant portionand said second implant portion further comprises: the ceramic layercomprises a secondary phase; and, the diffusion hardened zone has alayered structure comprising at least two distinct layers undermetallographic analysis, the layered structure characterized by: a firstlayer directly below the ceramic layer; an interface between the firstlayer and the ceramic layer; and; a second layer directly below thefirst layer.
 83. The medical implant of claim 80, wherein one or both ofsaid first implant portion and said second implant portion furthercomprises: a substrate; a diffusion hardened zone in contact with saidsubstrate, said diffusion hardened zone comprising a diffusion hardeningspecies, said diffusion hardened zone having a thickness of greater than5 microns; and, wherein the diffusion hardened zone has a layeredstructure comprising at least two distinct layers under metallographicanalysis, said layered structure characterized by: a first layer on asurface of the implant; a second layer directly below said first layer;and, said diffusion hardened zone having a concentration of diffusionhardening species which decreases in the direction of the substrate,said decrease of concentration of diffusion hardening species beingdefined by a function selected from the group consisting of an errorfunction, an exponential function, a near uniform distribution function,and any sequential combination thereof.
 84. The medical implant of claim80, wherein one or both of said first implant portion and said secondimplant portion further comprises: a substrate; a diffusion hardenedzone in contact with said substrate, said diffusion hardened zonecomprising a diffusion hardening species, said diffusion hardened zonehaving a thickness of greater than 2 microns; and, a substantiallydefect-free ceramic layer in contact with said diffusion hardened zoneand comprising a surface of said medical implant, said ceramic layerranging in thickness from 0.1 to 25 microns; and, wherein the totalthickness of the ceramic layer and the diffusion hardened zone is 5microns or greater.
 85. The medical implant of claim 80, wherein one orboth of said first implant portion and said second implant portionfurther comprises: the ceramic layer comprises a secondary phase; and,the diffusion hardened zone has a layered structure comprising at leasttwo distinct layers under metallographic analysis, the layered structurecharacterized by: a first layer directly below the ceramic layer; aninterface between the first layer and the ceramic layer; and; a secondlayer directly below the first layer.